Pantoea ananatis, a plant growth stimulating bacterium, and its metabolites isolated from Hydrocotyle umbellata (dollarweed).

A bacterium growing on infected leaves of Hydrocotyle umbellata, commonly known as dollarweed, was isolated and identified as Pantoea ananatis. An ethyl acetate extract of tryptic soy broth (TSB) liquid culture filtrate of the bacterium was subjected to silica gel chromatography to isolate bioactive molecules. Indole was isolated as the major compound that gave a distinct, foul odor to the extract, together with phenethyl alcohol, phenol, tryptophol, N-acyl-homoserine lactone, 3-(methylthio)-1-propanol, cyclo(L-pro-L-tyr), and cyclo(dehydroAla-L-Leu). This is the first report of the isolation of cyclo(dehydroAla-L-Leu) from a Pantoea species. Even though tryptophol is an intermediate in the indoleacetic acid (IAA) pathway, we were unable to detect or isolate IAA. We investigated the effect of P. ananatis inoculum on the growth of plants. Treatment of Lemna paucicostata Hegelm plants with 4 × 109 colony forming units of P. ananatis stimulated their growth by ca. five-fold after 13 days. After 13 days of treatment, some control plants were browning, but treated plants were greener and no plants were browning. The growth of both Cucumis sativus (cucumber) and Sorghum bicolor (sorghum) plants was increased by ca. 20 to 40%, depending on the growth parameter and species, when the rhizosphere was treated with the bacterium after germination at the same concentration. Plant growth promotion by Pantoea ananatis could be due to the provision of the IAA precursor indole.

Excess Enthalpies Analysis of Biofuel Components: Sunflower Oil-Alcohols Systems.

This study addresses the pressing issues of energy production and consumption, in line with global sustainable development goals. Focusing on the potential of alcohols as "green" alternatives to traditional fossil fuels, especially in biofuel applications, we investigate the thermochemical properties of three alcohols (n-propanol, n-butanol, n-pentanol) blended with sunflower oil. The calorimetric analysis allows for the experimental determination of excess enthalpies in pseudo-binary mixtures at 303.15 K, revealing similarities in the trends of the curves (dependence on concentrations) but with different values for the excess enthalpies for each mixture. Despite the structural differences of the alcohols studied, the molar excess enthalpy values exhibit uniformity, suggesting consistent mixing behavior. The peak values of excess enthalpies for systems with sunflower oil and n-propanol, n-butanol and n-pentanol are, respectively, 3255.2 J/mole, 3297.4 J/mole and 3150.1 J/mole. Both the NRTL and Redlich-Kister equations show satisfactory agreement with the obtained values.

Pectin Nanoporous Structures Prepared via Salt-Induced Phase Separation and Ambient Azeotropic Evaporation Processes.

Polysaccharide nanoporous structures are suitable for various applications, ranging from biomedical scaffolds to adsorption materials, owing to their biocompatibility and large surface areas. Pectin, in particular, can create 3D nanoporous structures in aqueous solutions by binding with calcium cations and creating nanopores by phase separation; this process involves forming hydrogen bonds between alcohols and pectin chains in water and alcohol mixtures and the resulting penetration of alcohols into calcium-bound pectin gels. However, owing to the dehydration and condensation of polysaccharide chains during drying, it has proven to be challenging to maintain the 3D nanoporous structure without using a freeze-drying process or supercritical fluid. Herein, we report a facile method for creating polysaccharide-based xerogels, involving the co-evaporation of water with a nonsolvent (e.g., a low-molecular-weight hydrophobic alcohol such as isopropyl or n-propyl alcohol) at ambient conditions. Experiments and coarse-grained molecular dynamics simulations confirmed that salt-induced phase separation and hydrogen bonding between hydrophobic alcohols and pectin chains were the dominant processes in mixtures of pectin, water, and hydrophobic alcohols. Furthermore, the azeotropic evaporation of water and alcohol mixed in approximately 1:1 molar ratios was maintained during the natural drying process under ambient conditions, preventing the hydration and aggregation of the hydrophilic pectin chains. These results introduce a simple and convenient process to produce 3D polysaccharide xerogels under ambient conditions.

Effects of different extraction methods on volatile profiles of flaxseed oils.

To investigate the effects of different extraction methods on volatile compounds in flaxseed oil (FSO), we first carried out solvent extraction, cold pressing, and hot pressing treatments of flaxseed [Linum usitatissimum (L.)], then applied the headspace-gas chromatography-ion mobility spectrometry technology to identify the volatile substance compositions, and established flavor fingerprints of solvent-extracted FSO, cold-pressed FSO, and hot-pressed FSO. In total, 81 volatile compounds were detected, including 27 aldehydes, 14 alcohols, 13 ketones, 9 heterocycles, 8 esters, 5 acids, 4 hydrocarbons, and 1 sulfur compound (dimethyl disulfide). Extraction methods had a great influence on the volatile profile of FSO. Solvent-extracted FSO had more sweet, mild, floral, and sour volatile profiles, cold-pressed FSO had stronger volatile profiles of winey, spicy, and fatty, and hot-pressed FSO had green, grass, and plastic volatile profiles. Principal component analysis and Euclidean distance demonstrated that the volatile compounds of three FSO samples could be clearly distinguished. Of note, the cold-pressed FSO and hot-pressed FSO had similar volatile profiles, and they were different from solvent-extracted FSO. This study could provide some guidance for improving the flavor quality of FSO and selecting the proper extraction method for FSO productions. PRACTICAL APPLICATION: Practical Application: This study shows extraction methods significantly affect the formation of aroma characteristics in flaxseed oil (FSO), and it provides theoretical guidance for production to use the appropriate extraction methods for high-quality FSO.

Chemometrics-based investigation of non-volatiles/volatiles flavor of tencha (Camellia sinensis cv. Yabukita, Longjing 43 and Baiye 1).

The increasing demand for tea consumption calls for the development of more products with distinct characteristics. The sensory quality of tencha is significantly determined by innate differences among tea cultivars. However, the correlations between the chemical composition and sensory traits of tencha are still unclear. To enhance the understanding of the flavor formation mechanism in tencha and further to develop new cultivars resources, we investigated non-volatiles and volatile metabolites as well as sensory traits in tencha from different tea cultivars (Camellia sinensis cv. Yabukita, Longjing 43 and Baiye 1); the relationships between the flavor traits and non-volatiles/volatiles were further evaluated by partial least squares - discriminate analysis (PLS-DA), multiple factor analysis (MFA) and multidimensional alignment (MDA) analysis. A total of 64 non-volatiles and 116 volatiles were detected in all samples, among which 71 metabolites were identified as key flavor-chemical contributors involving amino acids, flavonol glycosides, flavones, catechins, ketones, alcohols, hydrocarbons, aldehydes, esters and acids. The levels of taste-related amino acids, flavonol glycosides and gallic acid varied significantly among the tencha samples made from different tea cultivars. All the samples exhibited typical quality characteristics of tencha. The tencha from Camellia sinensis cv. Longjing 43 and Camellia sinensis cv. Baiye 1 (cultivated in the open) exhibited higher levels of amino acids and gallic acid, which were associated with the umami taste and mellow taste of tea infusion. Abundant flavonol glycosides were related to the astringency, while partial tri-glycosides specifically quercetin-3-O-galactoside-rhamnoside-glucoside and total of flavonol galactoside-rhamnoside-glucoside were associated with mellow taste. The floral alcohols were identified as significant contributors to the refreshing aroma traits of tencha. The green, almond-like, acidic and fruity odorants were associated with a green and fresh aroma, while the green, cheesy and waxy odorants such as ketones, esters, acids and hydrocarbons were associated with seaweed-like aroma. This study provides insight into sensory-related chemical profiles of tencha from different tea cultivars, supplying valuable information on flavor and quality identification for tencha.

Olive Fruit Ripening Degree and Water Content Relationships with Phenolic Acids and Alcohols, Secoiridoids, Flavonoids and Pigments in Fruit and Oil.

Olive drupe traits (i.e., ripening index and pericarp water content) and minor components (i.e., phenols and pigments in both fruit and oil) are important for human health and are affected by agronomic background. The aim of this study was to investigate the relationship between fruit traits, phenols, and pigments in samples derived from different soil and water management practices. Chromatographic (UHPLC-MS/MS) and spectroscopic (1HNMR and near UV-Vis spectroscopy) techniques were employed for the characterization of olive fruits and oils. The use of various techniques allowed the identification of interesting trace compounds. We observed that most of the fruit phenols (a total of 29 compounds) were correlated with the degree of ripening: most of the phenolic acids (and their derivatives), phenolic alcohols, and secoiridoids were negatively correlated, whereas the majority of the studied flavonoids were positively correlated. The relationship between the ripening index and fruit phenolic compounds appears to be dependent on the metabolic pathway that controls the synthesis of each individual compound. Conversely, the secoiridoids and pigments in olive oil showed a negative correlation with pulp moisture, probably because of the influence of the water content on the extractability and transfer in the oil phase of these minor components.

Catalytic Atroposelective Aerobic Oxidation Approaches to Axially Chiral Molecules.

A copper and chiral nitroxide co-catalyzed aerobic enantioselective oxidation process has been developed that allows access to axially chiral molecules. Two complementary atroposelective approaches, oxidative kinetic resolution (OKR) and desymmetrization, were studied using ambient air as the stoichiometric terminal oxidant. OKR of rac-N-arylpyrrole alcohols and rac-biaryl alcohols affords the optically pure compounds with er up to 3.5:96.5 and 5.5:94.5, respectively. Desymmetrization of prochiral diols provides axially chiral biaryl compounds with er up to 99:1.

Leaf cuticular waxes of wild-type Welsh onion (Allium fistulosum L.) and a wax-deficient mutant: Compounds with terminal and mid-chain functionalities.

Plant cuticles cover aerial organs to limit non-stomatal water loss and protect against insects and pathogens. Cuticles contain complex mixtures of fatty acid-derived waxes, with various chain lengths and diverse functional groups. To further our understanding of the chemical diversity and biosynthesis of these compounds, this study investigated leaf cuticular waxes of Welsh onion (Allium fistulosum L.) wild type and a wax-deficient mutant. Leaf waxes were extracted with chloroform, separated using thin layer chromatography (TLC), and analyzed using gas chromatography-mass spectrometry (GC-MS). The extracts contained typical wax compound classes found in nearly all plant lineages but also two uncommon compound classes. Analyses of characteristic MS fragmentation patterns followed by comparisons with synthetic standards identified the latter as very-long-chain ketones and primary ketols. The ketols were minor compounds, with chain lengths ranging from C28 to C32 and carbonyls mainly on C-18 and C-20 in wild type wax, and a C28 chain with C-16 carbonyl in the mutant. The ketones made up 70% of total wax in the wild type, consisting mainly of C31 isomers with carbonyl group on C-14 or C-16. In contrast, the mutant wax comprised only 4% ketones, with chain lengths C27 and C29 and carbonyls predominantly on C-12 and C-14, respectively. A two-carbon homolog shift between wild type and mutant was also observed in the primary alcohols (a major wax compound class), whilst alkanes exhibited a four-carbon shift. Overall, the compositional data shed light on possible biosynthetic pathways to wax ketones that can be tested in future studies.

Exploiting the Integrated Valorization of Eucalyptus globulus Leaves: Chemical Composition and Biological Potential of the Lipophilic Fraction before and after Hydrodistillation.

E. globulus leaves have been mainly exploited for essential oil recovery or for energy generation in industrial pulp mills, neglecting the abundance of valuable families of extractives, namely, triterpenic acids, that might open new ways for the integrated valorization of this biomass. Therefore, this study highlights the lipophilic characterization of E. globulus leaves before and after hydrodistillation, aiming at the integrated valorization of both essential oils and triterpenic acids. The lipophilic composition of E. globulus leaves after hydrodistillation is reported for the first time. Extracts were obtained by dichloromethane Soxhlet extraction and analyzed by gas chromatography-mass spectrometry. In addition, their cytotoxicity on different cell lines representative of the innate immune system, skin, liver, and intestine were evaluated. Triterpenic acids, such as betulonic, oleanolic, betulinic and ursolic acids, were found to be the main components of these lipophilic extracts, ranging from 30.63-37.14 g kg-1 of dry weight (dw), and representing 87.7-89.0% w/w of the total content of the identified compounds. In particular, ursolic acid was the major constituent of all extracts, representing 46.8-50.7% w/w of the total content of the identified compounds. Other constituents, such as fatty acids, long-chain aliphatic alcohols and ß-sitosterol were also found in smaller amounts in the studied extracts. This study also demonstrates that the hydrodistillation process does not affect the recovery of compounds of greatest interest, namely, triterpenic acids. Therefore, the results establish that this biomass residue can be considered as a promising source of value-added bioactive compounds, opening new strategies for upgrading pulp industry residues within an integrated biorefinery context.

Quality assessment of rose tea with different drying methods based on physicochemical properties, HS-SPME-GC-MS, and GC-IMS.

The purpose of this study is to compare the physicochemical properties and volatile flavor compounds of rose tea obtained by the methods of normal temperature drying, hot-air drying (HAD), and vacuum freeze-drying (VFD) and to evaluate the quality of rose tea. The physicochemical results showed that the content of ascorbic acid (VC) and the pH value was the highest in rose tea obtained by HAD. The contents of anthocyanin, proanthocyanidins, and total phenols were highest in rose tea obtained by VFD. However, there was no significant difference in total flavonoids between drying methods. The volatile organic compounds (VOCs) in rose tea with different drying methods were analyzed by headspace solid-phase microextraction-gas chromatography-mass spectroscopy (HS-SPME-GC-MS) and HS GC-ion mobility spectroscopy (HS-GC-IMS), and the flavor fingerprint of rose tea was established by principal component analysis (PCA). The concentration of VOCs in rose tea varied greatly with different drying methods. The main flavor compounds of rose tea were alcohols, esters, aldehydes, and terpenoids. HS-GC-IMS was used for the identification of volatile flavor compounds of rose tea, thereby helping to assess the quality of rose tea. In addition, the rose tea samples with different drying methods were well distinguished by PCA. This study deepens the understanding of the physicochemical properties and volatile flavor compounds of rose tea with different drying methods and provides a reference for the identification of rose tea with different drying methods. PRACTICAL APPLICATION: This study deepens the understanding of the physicochemical properties and volatile flavor compounds of rose tea with different drying methods and provides a reference for the identification of rose tea with different drying methods. It also provides an effective theoretical basis for consumers to buy rose tea.

Evolution of monovarietal virgin olive oils as a function of chemical composition and oxidation status.

Virgin Olive Oil (VOO) shelf life is determined by the varietal-specific chemical composition and principally by the of phenolic composition. The aim of this study was to investigate the changes in fatty acid profile, phenolic composition, and quality parameters of nine Italian monovarietal VOOs obtained under the same pedoclimatic, agronomic and technological conditions and stored for 12 months at 15 °C in the dark. The varieties with medium-high concentrations of secoiridoids and balanced values between the individual molecules were those with the highest stability. Orthogonal Projections to Latent Structures (OPLS) regression revealed that oleuropein derivatives and phenolic alcohols had the highest antioxidant activity. OPLS discriminant analysis separated well fresh and stored oils. PV, K270, tyrosol, hydroxytyrosol, and oxidated oleacein were the most effective indicators of VOO ageing. Oleacein and oleocanthal decreased after storage, phenolic alcohols, oleacein and ligstroside aglycon increased.

Determination of Characteristic Volatile Component Fingerprint of Peucedanum Praeruptorum Dunn at Different Harvest Periods Based on HS-GC-IMS.

BACKGROUND: Peucedanum praeruptorum Dunn (PPD) is a Chinese herbal medicine with medicinal value. Clinical studies have shown that PPD has protective effects against wind-heat, cough, asthma, cardiovascular diseases, and cancer. Therefore, cultivation of PPD is becoming more common. However, it has been difficult to determine the optimal harvest period for botanical Chinese medicines such as PPD. OBJECTIVES: Odor characteristics are directly related to the chemical components contained in traditional Chinese medicines. In particular, for traditional Chinese medicines such as PPD that are rich in volatile components, higher quality usually means more beneficial volatile components. The purpose of this study was to analyze changes in PPD volatile components across different harvest periods, and provide the basis for the identification of the ideal harvest period to ensure PPD quality. METHODS: We measured the volatile components of PPD at different harvest periods using HS-GC-IMS to characterize its volatile component fingerprint at different harvest periods. RESULTS: We identified 80 volatile components in PPD across five harvest periods, and combined complex heatmap and PCA methods distinguish the characteristics of the different harvest periods, and used ion mobility spectrometry to determine the volatile organic compounds (VOCs), which mainly included compounds such as olefins, esters, alcohols, aldehydes, and ketones, and determined that the abundance of volatile components reached a peak in December. CONCLUSIONS: The fingerprint determination of characteristic volatile components based on HS-GC-IMS can distinguish PPD in different harvest periods. HIGHLIGHTS: We used HS-GC-IMS to determine the characteristic fingerprint of volatile components from PPD across different harvest periods. This approach differs from past studies, which have determined the optimal harvest time of medicinal materials based on only the content of a single active ingredient.

Power ultrasound treatment of Viognier grapes as a tool to increase the aromatic potential of wines.

BACKGROUND: High-power ultrasound is a novel and non-thermal technique normally used in red vinification to increase the extraction of phenolic compounds. However, few studies have been carried out on its effect on the extraction of aroma compounds and their precursors in white grapes. This study evaluates the effect of high-power ultrasound at winery scale in the maceration of Viognier grapes on the content of varietal volatile compounds (free and glycosidically bound) in musts and wines, in comparison with wines from direct pressing and from short skin maceration. RESULTS: The pre-fermentative ultrasound treatment of the grapes produced an increase in most of the varietal compounds of musts and wines, both in the free fraction and in the bound one, especially in the C6 alcohols, terpenes and norisoprenoids, some of them of sensory relevance, while the effect on esters and lactones was less evident. Ultrasound maceration allowed us to obtain wines of higher aromatic intensity, with a more pronounced varietal character. CONCLUSION: The pre-fermentative ultrasound treatment of Viognier grapes increases the aromatic potential of the wines, as it favors the extraction of free and bound varietal volatile compounds. In addition, it allows the maceration time of the grapes to be reduced compared to conventional pre-fermentation techniques, thus avoiding oxidative processes that could negatively affect the aroma of the wines. © 2022 Society of Chemical Industry.

"Click" preparation of a chiral macrocycle-based stationary phase for both normal-phase and reversed-phase high performance liquid chromatography enantioseparation.

Chiral polyimine macrocycles (CPMs) constitute a new family of organic macrocycles that have defined cavities, rigid shapes, inherent chirality and multiple cooperative binding sites, and have shown great potential in diverse areas. However, the application of CPMs for high performance liquid chromatography (HPLC) enantioseparation has rarely been reported. In this work, a novel chiral stationary phase (CSP) for HPLC was prepared by chemical bonding of a CPM (C54H72N6O3) onto thiolated silica via thiol-ene click reaction. The CSP exhibited good enantioselectivity in both normal- and reversed-phase HPLC. Chiral compounds included alcohols, diols, ketones, organic acids, esters, ethers, amines, and epoxides were enantioseparated on the column in normal-phase mode (17 compounds) and reversed-phase mode (20 compounds). Importantly, broader chiral resolution was observed with the column than that obtained using our previously studied chiral macrocycle H3L-based column, indicating the potential to significantly improve and broaden applicability of this novel macrocycle-type CSPs. Moreover, the CSP exhibited good complementary enantioseparation to Chiralpak AD-H and Chiralcel OD-H columns, enabling separation of some racemates that could not be separated by the two popular chiral HPLC columns. In addition, the fabricated column exhibited good stability and reproducibility. The relative standard deviations (RSDs) (n = 5) of retention time and resolution after multiple injections were < 0.20 % and < 0.39 %, respectively. The results demonstrated the great potential of this type of CPM for HPLC separation of enantiomers.

Emissions of Fungal Volatile Organic Compounds in Residential Environments and Temporal Emission Patterns: Implications for Sampling Methods.

Currently, little is known about the occurrences of fungi-derived microbial volatile organic compounds (mVOCs) in various indoor materials and their detection in residential environments, despite mVOCs being linked to several acute health effects. We identified various mVOCs emitted from fungi grown on PVC wallpaper, silicone rubber, and malt extract agar. We also investigated mVOCs temporal emission and whether fungi-derived VOCs concentration can be used to estimate fungal concentration in the air using active and passive air sampling methods. Among the three fungal growth media included in this study, silicone rubber produced the most variety of mVOCs: 106 compounds (from Aspergillus niger), 35 compounds (from Alternaria alternata), and 85 compounds (from Penicillium chrysogenum). We also found the emission patterns of eight chemical classes (i.e., aromatics, ethers, aliphatics, alcohols, ketones, aldehydes, chlorides, and nitrides) from the three different fungi. From the results of our field experiments in 11 residential environments, passive air samplers led to higher correlations coefficients (0.08 to 0.86) between mVOCs' air concentrations and airborne fungal concentrations, compared with active air samplers, which showed negative correlation coefficients (-0.99 to -0.02) for most compounds. This study elucidated the occurrence and temporal emission patterns of fungal VOCs in residential environments.

Lipophilic Compounds and Antibacterial Activity of Opuntia ficus-indica Root Extracts from Algeria.

The chemical composition, investigated by gas chromatography-mass spectrometry, and antibacterial activity of lipophilic extractives of three varieties of Opuntia ficus-indica roots from Algeria are reported in this paper for the first time. The results obtained revealed a total of 55 compounds, including fatty acids, sterols, monoglycerides and long chain aliphatic alcohols that were identified and quantified. ß-Sitosterol was found as the major compound of the roots of the three varieties. Furthermore, considerable amounts of essential fatty acids (ω3, ω6, and ω9) such as oleic, linoleic, and linolenic acids were also identified. The green variety was the richest among the three studied varieties. The antibacterial activity, evaluated with disc diffusion method, revealed that lipophilic extracts were effective mainly against Gram-positive Staphylococcus aureus and methicillin-resistant Staphylococcus aureus (MRSA) (19~23 mm). Gram-negative strains mainly Pseudomonas aeruginosa gave an inhibition zone of 18 mm, which is considered high antibacterial activity. The minimal inhibitory concentrations of the tested bacteria revealed interesting values against the majority of bacteria tested: 75-100 µg mL-1 for Bacillus sp., 250-350 µg/mL for the two Staphylococcus strains, 550-600 µg mL-1 for E. coli, and 750-950 µg mL-1 obtained with Pseudomonas sp. This study allows us to conclude that the lipophilic fractions of cactus roots possess interesting phytochemicals such as steroids, some fatty acids and long chain alcohols that acted as antibiotic-like compounds countering pathogenic strains.

Nanolipogel Loaded with Tea Tree Oil for the Management of Burn: GC-MS Analysis, In Vitro and In Vivo Evaluation.

The GC-MS analysis of tea tree oil (TTO) revealed 38 volatile components with sesquiterpene hydrocarbons (43.56%) and alcohols (41.03%) as major detected classes. TTO efficacy is masked by its hydrophobicity; nanoencapsulation can address this drawback. The results showed that TTO-loaded solid lipid nanoparticles (SLN1), composed of glyceryl monostearate (2% w/w) and Poloxamer188 (5% w/w), was spherical in shape with a core-shell microstructure. TTO-SLN1 showed a high entrapment efficiency (96.26 ± 2.3%), small particle size (235.0 ± 20.4 nm), low polydispersity index (0.31 ± 0.01), and high negative Zeta potential (-32 mV). Moreover, it exhibited a faster active agent release (almost complete within 4 h) compared to other formulated TTO-SLNs as well as the plain oil. TTO-SLN1 was then incorporated into cellulose nanofibers gel, isolated from sugarcane bagasse, to form the 'TTO-loaded nanolipogel' which had a shear-thinning behavior. Second-degree thermal injuries were induced in Wistar rats, then the burned skin areas were treated daily for 7 days with the TTO-loaded nanolipogel compared to the unmedicated nanolipogel, the TTO-loaded conventional gel, and the normal saline (control). The measurement of burn contraction proved that TTO-loaded nanolipogel exhibited a significantly accelerated skin healing, this was confirmed by histopathological examination as well as quantitative assessment of inflammatory infiltrate. This study highlighted the success of the proposed nanotechnology approach in improving the efficacy of TTO used for the repair of skin damage induced by burns.

Iodine-Mediated Alkoxyselenylation of Alkenes and Dienes with Elemental Selenium.

A one-pot synthesis of linear and cyclic ß-alkoxyselenides is developed through the iodine-mediated three-component reaction of elemental selenium with alkenes (dienes) and alcohols. Selenylation of 1,5-hexadiene gives 2,5-di(methoxymethyl)tetrahydroselenophene and 2-methoxy-6-(methoxymethyl)tetrahydro-2H-selenopyran via the 5-exo-trig and 6-endo-trig cyclization. 1,7-Octadiene affords only linear 1:2 adduct with two terminal double bonds. 1,5-Cyclooctadiene results in one diastereomer of 2,6-dialkoxy-9-selenabicyclo [3.3.1]nonanes via 6-exo-trig cyclization. With 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane, the first ring-substituted representative of a very rare class of heterocycles, 1,4,2,6-oxaselenadisilinanes, was obtained at a high yield.

Near-UV and Visible Light Degradation of Iron (III)-Containing Citrate Buffer: Formation of Carbon Dioxide Radical Anion via Fragmentation of a Sterically Hindered Alkoxyl Radical.

Citrate is a commonly used buffer in pharmaceutical formulations which forms complexes with adventitious metals such as Fe3+. Fe3+-citrate complexes can act as potent photosensitizers under near-UV and visible light exposure, and recent studies reported evidence for the photo-production of a powerful reductant, carbon dioxide radical anion (•CO2-), from Fe3+-citrate complexes (Subelzu, N.; Schöneich, N., Mol. Pharm. 2020, 17, 4163-4179). The mechanisms of •CO2- formation are currently unknown but must be established to devise strategies against •CO2- formation in pharmaceutical formulations which rely on the use of citrate buffer. In this study, we first established complementary evidence for the photolytic generation of •CO2- from Fe3+-citrate through spin trapping and electron paramagnetic resonance (EPR) spectroscopy, and subsequently used spin trapping in conjunction with tandem mass spectrometry (MS/MS) for mechanistic studies on the pathways of •CO2- formation. Experiments with stable isotope-labeled citrate suggest that the central carboxylate group of citrate is the major source of •CO2-. Competition studies with various inhibitors (alcohols and dimethyl sulfoxide) reveal two mechanisms of •CO2- formation, where one pathway involves ß-cleavage of a sterically hindered alkoxyl radical generated from the hydroxyl group of citrate.

Insecticidal effect of Eucalyptus globulus and Rosmarinus officinalis essential oils on a stored food pest Ephestia kuehniella (Lepidoptera, Pyralidea).

For the purpose of evaluating the local heritage of eastern Numidia, an ethnobotanical survey was conducted on a population located in the province (department) of El-Tarf (North-East of Algeria) on a frequency of use of two plants known in traditional health; Eucalyptus globulus (Myrtaceae) and Rosmarinus officinalis (Lamiaceae). After processing data, our results show a female dominance when using these plants on a fairly advanced age group (40 to 60 years old). These plants are used by the people at their fresh state and deem the leaf as the most used part for therapeutic and cosmetic purposes. Furthermore, steam baths and infusion remain the most widespread preparation methods. Most consumers use these plants to treat influenza, respiratory illnesses as well as diseases of the digestive tract. GC-MS of essential oils extracted from the plants studied disclose a dominance of the alcohols portrayed by the monoterpenes (42.73%), sesquiterpenes (32.6%) and oxides (10.48%) in E. globulus. Data also indicate a high content of oxides (38.11%) monoterpene alcohols (20.43%) and monoterpenes (19.70%) in R.officinalis. Toxicological contact tests were achieved on a store-products pest Ephestia kuehniella. The test results were assessed with E.globulus (LC50=0.013; LC95=0.081 µl/cm2) and R.officinalis (LC50=0.011; LC95=0.059 µl/cm2). The lethal time changes according to the dose used and the tested plant. In E.globulus, we observe (concentration: 0.005 µl/cm2; LT50=56.2 h), (Concentration: 0.01 µl/cm2; LT50=49.53h) and (Concentration: 0.04µl/cm2; LT50=20.93h). Whereas in R.officinalis, we recorded (Concentration: 0.005 µl/cm2; LT50=55.7h), (Concentration: 0.01µl/cm2; LT50=54.99 h) and (Concentration: 0.04µl/cm2; LT50=29.13 h). The bioinsecticide has also been administered by fumigation and underpins toxicity by the reduction of adults longevity in E.kuehniella with R.officinalis (LC50=4.03 µl/l air; LC95=14.73 µl/l air) and E.globulus (LC50=7.76 µl/lair; LC95=21.23 µl/l air). In addition, the tested plants show an outstanding repellent effect as long as E.globulus and  R.officinalis essential oils respectively demonstrate a slightly repellent power at 42.22% (RD50=0.09 µl/cm2 ; RD95=0.24 µl/cm2) and repellent at 60.00% (RD50=0.06 µl/cm2 ; RD95= 0.35 µl/cm2) towards E.kuehniella adults. The plant resources represent a genuine reserve of bioactive molecules, which can create solutions to sustainable development issues. These plants might be the source of new molecules of combat against some pests in order to protect human health and safeguard the environment.