Selective Extraction of Bioactive Phenylethanoids from Digitalis obscura

Cardenolide-free extracts from Digitalis obscura showed significant antifeedant effects against the aphid Myzus persicae and this activity correlated with their phenylethanoid content. The content in phenylethanoids of Digitalis obscura has been studied. Maceration of the aerial parts of D. obscura was used for the selective extraction of the natural compound rengyolone (1) and the aglycone of cornoside (compound 3). Pure rengyolone (1) can be obtained from D. obscura in approximately 90% purity from fresh plant from the CHCl3 soluble fraction of the ethanolic extract (0.8% yield). The ethanol extraction of freshly collected D. obscura showed the presence of compound 3 as the only phenylethanoid. Compound 3 was proven to easily evolve to rengyolone. Due to this instability, and although its presence in plants has been previously reported, the spectroscopical data of 3 are reported herein for the first time. Selective mono-acetylation of compound of 3 led to the active natural compound hallerone (5). The aphid antifeedant (against Myzus persicae) and nematicidal (against root-knot nematode Meloidogyne javanica) activities of these compounds have been evaluated. Here we report for the first time on the aphid antifeedant effects of 1, 3, and 5. Additionally, the nematicidal activity of hallerone (5) is described here for the first time.MINISTERIO DE ECONOMÍA Y COMPETITIVIDADPID2019-106222RB-C32/SRA (State Research Agency, 10.13039/501100011033)PID2019- 106222RB-C31/SRA (State Research Agency, 10.13039/501100011033)ERASMUS + N◦2018-1-FR01- KA202-047892 Biocontrol E Training (BET)Unidad Asociada UGR-CSIC Bioplaguicidas: Biotecnología, síntesis y diversidad químic

Bioinspired Synthesis of Platensimycin from Natural ent-Kaurenoic Acids

Ministerio de Economía y Competitividad, PID2019-106222RB-C32/SRA (State Research Agency, 10.13039/501100011033)Universidad de Granada/CBU

Article Germacrone Derivatives as new Insecticidal and Acaricidal Compounds: A Structure-Activity Relationship

The supplementary material related to this article includes NMR spectra of new compounds is available online at https://www.mdpi.com/1420-3049/24/16/2898/s1.Currently, the use of synthetic pesticides is the main method of plant protection applied in agri- and horticulture. However, its excessive use leads to the development of pesticide resistance, a contamination of the environment, toxicity to non-target organisms, and risks for human health. With the ultimate aim of contributing to the develop of a more sustainable pest management, we used the natural product germacrone (compound 1), reported to possess significant insecticidal activity, as starting material for the generation of molecular diversity (2–24). Some of the generated derivatives are natural compounds, such as 1,10-epoxygermacrone (2), 4,5-epoxygermacrone (3), gajutsulactone A (7), germacrol (11), isogermacrone (14), 9-hydroxyeudesma-3,7(11)dien-6-one (19), eudesma-4,7(11),dien-8-one (20), eudesma-3,7(11)-dien-8-one (21) and eudesma-4(15),7(11)-dien-8-one (22). Compounds, 7,11-9,10-diepoxigermacr-4,5-en-8-ol (17), 7,11-epoxieudesma-4,7(11)-dien-8-one (23) and 7,11-epoxieudesma-3,7(11)-dien-8-one (24) are described for the first time. The biocidal activity of most of these compounds was assayed against the tick Hyalomma lusitanicum. The acaricidal effects of compound 24 were four times higher than that of germacrone (1). Compound 2 is an insect antifeedant a thousand times more potent than germacrone against Rhopalosiphum padi, which makes this substance a promising selective antifeedant against this cereal pest.This research was funded by Grant CTQ-2015-64049-C3-3-R/CTQ2015-64049-C3-1-R; MINISTERIO DE ECONOMÍA Y COMPETITIVIDAD, Spain (MINECO/FEDER)

Valorization of the Sabinas Forest Waste (Juniperus phoenicea and Juniperus thurifera) as Source of Biopesticides

Objectives: The potential forestry use of Juniperus phoenicea and Juniperus thurifera pruning woods is studied by analyzing the composition of the woods and testing the biological activities of the corresponding components with the ultimate target of finding new biopesticides. Methods: The air-dried wood from each plant was crushed and subjected to hydrodistillation, and the residue was extracted with a Soxhlet apparatus using different solvents. The corresponding extracts were fractionated, and their composition were studied by gas chromatography-mass spectrometry and nuclear magnetic resonance techniques. The ixodicidal and antifungal activities of the different samples obtained were evaluated. Results: The fraction oxygenated of the essential oil from both J. thurifera (cedrol >60%) and J. phoenicea shows a remarkable bioactivity as antitick with EC50 values of 3.4 μg/mg and 10 μg/mg, respectively. Cedrol and methyl hinokiate, present in the hexane extract J. thurifera, show a potent antifungal effect against Aspergillus niger with EC50 values of 45.99 and 52.23 μg/mL, respectively. Conclusions: Pruning woods from these species proved to be renewable and easily accessible sources of bioactive natural products such as cedrol, thujopsene, nootkatone, and totarol.MINISTERIO de CIENCIA e INNOVACIÓN, PID2019-106222RB-C31/SRA, PID2019-106222RBC32/ SRA (State Research Agency, 10.13039/501100011033)Unidad Asociada UGR-CSIC Bioplaguicidas: Biotecnología, Síntesis y Diversidad químic

Diclofenac N-Derivatives as Therapeutic Agents with Anti-Inflammatory and Anti-Cancer Effect

A series of diclofenac N-derivatives (2, 4, 6, 8c, 9c, 10a-c) were synthesized in order to test their anti-cancer and anti-inflammatory effects. The anticarcinogen activity has been assayed against three cancer cell lines: HT29, human colon cancer cells; Hep-G2, human hepatic cells; and B16-F10, murine melanoma cells. First, we determined the cytotoxicity of the different compounds, finding that the most effective compound was compound 8c against all cell lines and both compounds 4 and 6 in human Hep-G2 and HT29 cell lines. Compounds 4 and 8c were selected for the percentage of apoptosis determination, cell cycle distribution, and mitochondrial membrane potential measure because these products presented the lowest IC50 values in two of the three cancer cell lines assayed (B16-F10 and HepG2), and were two of the three products with lowest IC50 in HT29 cell line. Moreover, the percentages of apoptosis induction were determined for compounds 4 and 8c, showing that the highest values were between 30 to 60%. Next, the effects of these two compounds were observed on the cellular cycle, resulting in an increase in the cell population in G2/M cell cycle phase after treatment with product 8c, whereas compound 4 increased the cells in phase G0/G1, by possible differentiation process induction. Finally, to determine the possible apoptosis mechanism triggered by these compounds, mitochondrial potential was evaluated, indicating the possible activation of extrinsic apoptotic mechanism. On the other hand, we studied the anti-inflammatory effects of these diclofenac (DCF) derivatives on lipopolysaccharide (LPS) activated RAW 264.7 macrophagesmonocytes murine cells by inhibition of nitric oxide (NO) production. As a first step, we determined the cytotoxicity of the synthesized compounds, as well as DCF, against these cells. Then, sub-cytotoxic concentrations were used to determine NO release at different incubation times. The greatest antiinflammatory effect was observed for products 2, 4, 8c, 10a, 10b, and 9c at 20 µg·mL−1 concentration after 48 h of treatment, with inhibition of produced NO between 60 to 75%, and a concentration that reduces to the 50% the production of NO (IC50 NO) between 2.5 to 25 times lower than that of DCF. In this work, we synthesized and determined for the first time the anti-cancer and anti-inflammatory potential of eight diclofenac N-derivatives. In agreement with the recent evidences suggesting that inflammation may contribute to all states of tumorigenesis, the development of these new derivatives capable of inducing apoptosis and anti-inflammatory effects at very low concentrations represent new effective therapeutic strategies against these diseases.MINISTERIO DE ECONOMÍA Y COMPETITIVIDAD, PID2019-106222RB-C32/SRA (State Research Agency, 10.13039/501100011033)“Consejería de Economía, Conocimiento, Empresas y Universidad. Junta de Andalucía”, grant number B1-BIO-281-UGR1

Selectivity of Relative Humidity Using a CP Based on S-Block Metal Ions

Herein, we present the syntheses of a novel coordination polymer (CP) based on the perylene-3,4,9,10-tetracarboxylate (pery) linkers and sodium metal ions. We have chosen sodium metal center with the aim of surmising the effect that the modification of the metal ion may have on the relative humidity (RH) experimental measurements of the material. We confirm the role of the ions in the functionalization of the deposited layer by modifying their selectivity towards moisture content, paving the way to the generation of sensitive and selective chemical sensors.This work is part of the I+D+I projects PGC2018-102052-A-C22, PGC2018-102052-B-C21, PID2020-117344R-I00 and CTQ-2015-64049-C3-3R, supported by the MCIN/AEI/10.13039/501100011033/ (FEDER: A way to make Europe), Junta de Andalucía (FQM-394, P20_00265 and B-FQM-734-UGR20). It also has been supported by the European Commission through the fellowship H2020-MSCA-IF-2017 794885-SELFSENS.Peer reviewe

Procedimiento de obtención de mirrhanol y derivados

Número de publicación: ES2391735 B1. Número de solicitud: 201231165.La presente invención describe un procedimiento para la preparación de uno o más de los siguientes: compuestos seleccionado del grupo formado por (+)-mirrhanol C, (+)-mirrhanol A, (+)-mirrhanona A, (+)-mirrhanona B y (+)-mirrhanol B, que comprende una etapa de biotransformación del compuesto drimanodiol I con un hongo filamentoso para dar un nuevo intermedio de síntesis, el compuesto 7a, a partir del cual se obtiene el compuesto 6 que se condensa con el compuesto 9 por reacción de Suzuki-Miyaura. La invención se refiere asimismo a este nuevo compuesto y a un procedimiento para la transformación del producto secundario de la biotransformación, el compuesto 7b, en el 7a.Universidad de Granad

Novel Insect Antifeedant and Ixodicidal Nootkatone Derivatives

© The Author(s).Naturally occurring nootkatone, with reported insecticidal and acaricidal properties, has been used as a lead to generate molecular diversity and, consequently, new insect antifeedant and ixodicidal compounds. A total of 22 derivatives were generated by subjecting this molecule to several reactions including dehydrogenation with the iodine/DMSO system, oxidation with SeO2, epoxidation with mCPBA, oxidation or carbon homologations of the α-carbonyl position with TMSOTf (trimethylsilyl trifluoromethanesulfonate) followed by Rubottom and Dess Martin periodane oxidations, condensation with formaldehyde using Yb(OTf)3 as catalyst and dehydroxilation using the Grieco protocol. The insect antifeedant (against Myzus persicae and Ropaloshysum padi) and ixodicidal (against the tick Hyalomma lusitanicum) activities of these compounds were tested. Compound 20 was the most active substance against M. persicae and R. padi, and twice more efficient than nootkatone in the antitick test.This research was funded by Grant CTQ-2015-64049-C3-3-R / CTQ2015-64049-C3-1-R; Ministerio de Economía y Competitividad, Spain (MINECO/FEDER).Peer reviewe

Selective Extraction of Bioactive Phenylethanoids from Digitalis obscura

Cardenolide-free extracts from Digitalis obscura showed significant antifeedant effects against the aphid Myzus persicae and this activity correlated with their phenylethanoid content. The content in phenylethanoids of Digitalis obscura has been studied. Maceration of the aerial parts of D. obscura was used for the selective extraction of the natural compound rengyolone (1) and the aglycone of cornoside (compound 3). Pure rengyolone (1) can be obtained from D. obscura in approximately 90% purity from fresh plant from the CHCl3 soluble fraction of the ethanolic extract (0.8% yield). The ethanol extraction of freshly collected D. obscura showed the presence of compound 3 as the only phenylethanoid. Compound 3 was proven to easily evolve to rengyolone. Due to this instability, and although its presence in plants has been previously reported, the spectroscopical data of 3 are reported herein for the first time. Selective mono-acetylation of compound of 3 led to the active natural compound hallerone (5). The aphid antifeedant (against Myzus persicae) and nematicidal (against root-knot nematode Meloidogyne javanica) activities of these compounds have been evaluated. Here we report for the first time on the aphid antifeedant effects of 1, 3, and 5. Additionally, the nematicidal activity of hallerone (5) is described here for the first time

Derivados de germacroma para el control de plagas

[EN] The invention relates to germacrone derivatives that exhibit biocidal activity and can be used as antifeedants. In particular, it has been proven that these derivatives exhibit greater activity than germacrone in relation to certain types of mites and insects[ES] La presente invención se refiere a derivados de germacrona que presentan actividad biocida y como inhibidores del apetito. En particular, se ha comprobado que estos derivados presentan mayor actividad que germacrona frente a algunos tipos ácaros e insectos[FR] La présente invention concerne des dérivés de germachrome qui présentent une activité biocide et sont utiles comme inhibiteurs de l'appétit. En particulier, on a constaté que ces dérivés présentent une meilleure activité que le germachrome face à certains types d'acariens et d'insectesPeer reviewedUniversidad de Granada, Consejo Superior de Investigaciones Científicas (España), Universidad Complutense de MadridA1 Solicitud de patente con informe sobre el estado de la técnic