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The world of elite sports has always been characterized by intense competition, where victories are often determined by minimal differences. This means that every little detail in the preparation of top-level athletes is crucial to their performance at the highest level. One of the most significant aspects to monitor is the jumping capacity, as it enables the measurement of performance, progression, and helps prevent injuries. Herein, we present the development of a system capable of measuring the flight time and height reached by the user, reporting the results through a smartphone using an Android ad-hoc application, which handles all the data processing. The system consists of an affordable and portable circuit based on an accelerometer. It communicates with the smartphone via UART using a Bluetooth module, and its battery provides approximately 9 h of autonomy, making it suitable for outdoor operations. To evaluate the system’s precision, we conducted performance tests (counter-movement jumps) with seven subjects. The results confirmed the system’s potential for monitoring high-level sports training sessions, as the average deviation obtained was only 2.1% (~0.01 s) in the analysis of flight time and 4.6% (~0.01 m) in jump height.

We performed mutagenesis on a regular isoprenyl diphosphate synthase (IDS), neryl diphosphate synthase from Solanum lycopersicum (SlNPPS), that has a structurally related analogue performing non-head-to-tail coupling of two dimethylallyl diphosphate (DMAPP) units, lavandulyl diphosphate synthase from Lavandula x intermedia (LiLPPS). Wild-type SlNPPS catalyses regular coupling of isopentenyl diphosphate (IPP) and DMAPP in cis-orientation resulting in the formation of neryl diphosphate. However, if the enzyme is fed with DMAPP only, it is able to catalyse the coupling of two DMAPP units and synthesizes two irregular monoterpene diphosphates; their structures were elucidated by the NMR analysis of their dephosphorylation products. One of the alcohols is lavandulol. The second compound is the trans-isomer of planococcol, the first example of an irregular cyclobutane monoterpene with this stereochemical configuration. The irregular activity of SlNPPS constitutes 0.4 % of its regular activity and is revealed only if the enzyme is supplied with DMAPP in the absence of IPP. The exchange of asparagine 88 for histidine considerably enhanced the non-head-to-tail coupling. While still only observed in the absence of IPP, irregular activity of the mutant reaches 13.1 % of its regular activity. The obtained results prove that regular IDS are promising starting points for protein engineering aiming at the development of irregular activities and leading to novel monoterpene structures.

This research has been funded by Junta de Andalucía (Spain) under project B-TIC-468- UGR18. The project was partially supported by European Regional Development Funds (ERDF)., In skiing it is important to know how the skier accelerates and inclines the skis during the turn to avoid injuries and improve technique. The purpose of this pilot study with three participants was to develop and evaluate a compact, wireless, and low-cost system for detecting the inclination and acceleration of skis in the field based on inertial measurement units (IMU). To that end, a commercial IMU board was placed on each ski behind the skier boot. With the use of an attitude and heading reference system algorithm included in the sensor board, the orientation and attitude data of the skis were obtained (roll, pitch, and yaw) by IMU sensor data fusion. Results demonstrate that the proposed IMU-based system can provide reliable low-drifted data up to 11 min of continuous usage in the worst case. Inertial angle data from the IMU-based system were compared with the data collected by a video-based 3D-kinematic reference system to evaluate its operation in terms of data correlation and system performance. Correlation coefficients between 0.889 (roll) and 0.991 (yaw) were obtained. Mean biases from -1.13 degrees (roll) to 0.44 degrees (yaw) and 95% limits of agreements from 2.87 degrees (yaw) to 6.27 degrees (roll) were calculated for the 1-min trials. Although low mean biases were achieved, some limitations arose in the system precision for pitch and roll estimations that could be due to the low sampling rate allowed by the sensor data fusion algorithm and the initial zeroing of the gyroscope., Junta de Andalucia European Commission B-TIC-468UGR18, European Commission

Plant-based bioproduction of insect sex pheromones has been proposed as an innovative strategy to increase the sustainability of pest control in agriculture. Here, we describe the engineering of transgenic plants producing (Z) -11-hexadecenol (Z11-16OH) and (Z) -11-hexadecenyl acetate (Z11-16OAc), two main volatile components in many Lepidoptera sex pheromone blends. We assembled multigene DNA constructs encoding the pheromone biosynthetic pathway and stably transformed them into Nicotiana benthamiana plants. The constructs contained the Amyelois transitella AtrΔ11 desaturase gene, the Helicoverpa armigera fatty acyl reductase HarFAR gene, and the Euonymus alatus diacylglycerol acetyltransferase EaDAct gene in different configurations. All the pheromone-producing plants showed dwarf phenotypes, the severity of which correlated with pheromone levels. All but one of the recovered lines produced high levels of Z11-16OH, but very low levels of Z11-16OAc, probably as a result of recurrent truncations at the level of the EaDAct gene. Only one plant line (SxPv1.2) was recovered that harboured an intact pheromone pathway and which produced moderate levels of Z11-16OAc (11.8 μ g g -1 FW) and high levels of Z11-16OH (111.4 μ g g -1 ). Z11-16OAc production was accompanied in SxPv1.2 by a partial recovery of the dwarf phenotype. SxPv1.2 was used to estimate the rates of volatile pheromone release, which resulted in 8.48 ng g -1 FW per day for Z11-16OH and 9.44 ng g -1 FW per day for Z11-16OAc. Our results suggest that pheromone release acts as a limiting factor in pheromone biodispenser strategies and establish a roadmap for biotechnological improvements.

Mating disruption (MD) is widely used against the European grapevine moth (EGVM), Lobesia botrana (Denis and Schifferm&uuml, ller, Lepidoptera: Tortricidae), by installing passive dispensers or aerosol devices. The present work reports a new sampling and quantification methodology to obtain absolute data about field airborne pheromone concentration based on air samplings and sensitive chromatographic-spectroscopic methods. Samplings were performed in fields treated with passive dispensers or aerosol devices at different moments throughout the crop cycle to study how they act and how the disruption is triggered. Moreover, pheromone adsorption and releasing capacity of vine leaves were studied to elucidate their role in the disruption. Although both types of dispensers were effective in limiting the damage inflicted by EGVM, they performed differently and provided different airborne pheromone concentration profiles. Results also proved that leaves were able to adsorb and release part of the airborne pheromone acting as subsequent and additional pheromone sources. This fact could explain the different concentration profiles. Moreover, our results suggest that lower pheromone emission than that of the current passive dispensers still could provide an adequate performance in the field. Competitive mechanisms involved in MD using both dispensers, the dynamics of the airborne pheromone throughout the time and the importance of the canopy are discussed.

[EN] Native to sub-Saharan Africa, Delottococcus aberiae De Lotto (Hemiptera: Pseudoccidae) is an invasive mealybug that has been recently reported in Europe, seriously damaging citrus production in eastern Spain. In this study, we isolated and determined the structure of the sex pheromone of D. aberiae, to provide a highly specific and effective lure for detecting, monitoring, and potentially controlling this pest. The volatile profile of D. aberiae virgin and mated females was studied by aeration and collection of effluvia in Porapak-Q The resulting extracts were analyzed by gas chromatography coupled to mass spectrometry (GC-MS), revealing a candidate compound specific of virgin females. GC-MS and nuclear magnetic resonance spectroscopy data evidenced a new compound, (4,5,5-trimethyl-3-methylenecyclopent-1-en-1-yl)methyl acetate, with an unusual beta-necrodol skeleton. This compound was synthesized and shown to be attractive to male D. aberiae in both laboratory and field experiments. A GC analysis using an enantioselective stationary phase and polarimetry analyses of the synthetic enantiomers showed the natural compound emitted by virgin females to be the - enantiomer., This work received funding from Universitat Politecnica de Valencia (postdoctoral contract for SV) and Conselleria de Agricultura, Medio Ambiente, Cambio Climaico y Desarrollo Rural (Generalitat Valenciana) under grant agreement (S8456000)

[EN] The four-spotted coconut weevil, Diocalandra frumenti Fabricius (Coleoptera: Dryophthoridae), is a small weevil found attacking economically important palm species, such as coconut, date,, oil, and Canary palms. Given the scarcity of detection and management tools for this pest, the availability of a pheromone to be included in trapping protocols would be a crucial advantage. Previous laboratory experiments showed evidence for aggregation behavior; thus, our main goal was to identify the aggregation pheromone in this species. The volatile profile of D. frumenti individuals was studied by aeration and collection of effluvia in Porapak-Q and also by solid phase microextraction (SPME) techniques. Moreover, solvent extraction of previously frozen crushed individuals was also performed. All resulting extracts and SPME fibers were analyzed by gas chromatography coupled to mass spectrometry (GC-MS). The comparison of male and female samples provided the candidate compound, 5ethyl-2,4-dimethy1-6,8-dioxabicyclo [3.2.1]octane (multistriatin), whose biological activity was evaluated in olfactometer and field assays., This work received funding from Direccion General de Agricultura del Gobierno de Canarias (Spain).

Communication., A new family of stable layered organic–inorganic materials has been prepared, in one-step solvothermal process. They are based on an ordered nickel cluster-type nanoribbons separated from each other by specific alkyl (heptyl- or dodecyl-) arylic mono-carboxylate moieties acting as molecular spacers, perpendicular to the 1D inorganic chains. These organic spacers contain hydrocarbon tails with different length which control the separation level between inorganic 1D sub-units, inhibiting the 3D growth of conventional DUT-8-type metal–organic frameworks (MOFs). The lamellar nature of the materials formed was studied and confirmed by different characterization techniques, showing the structural location of individual organic and inorganic building units. They have been successfully used as a long-lasting biodegradable and water-proof materials for controlled release of chemicals, such as pheromones for sustainable treatment of insect plagues., The support of the European Union (ERC‐AdG‐2014‐671093—SynCatMatch) and the Spanish Government (MAT2014‐52085‐C2‐1‐P and Severo Ochoa program SEV‐2012‐0267) is acknowledged.

This work describes a synthetic approach to the carbocyclic skeleton of isospongian diterpenes that uses the commercially available monoterpene (S)-carvone as a C-ring synthon, which is incorporated into the tetracyclic isospongian framework via a C -> ABC -> ABCD ring annulation strategy using intramolecular Diels-Alder and ring-closing metathesis reactions. This approach has been successfully used to prepare both the title natural isospongians and several nonnatural oxygenated analogues. A preliminary evaluation of the inhibitory activity of the small collection of synthesized isospongians on the mammalian mitochondrial respiratory chain revealed that most were able to inhibit the integrated electron transfer chain (NADH oxidase activity) in the micromolar range., We thank the Spanish Ministerio de Ciencia e Innovacion (MICINN) and the company EPA S.L. (Cadet, Spain) for their continuous support of our work (Projects BQU2002-00272 and AGL2009-12940-C02-02). We also thank the S.C.S.I.E. of the University of Valencia for providing access to their NMR facilities and E. Estornell and V. Romero for biological assay support.

The aim of this study was to determine the vasorelaxant activity of a natural diterpene extracted from Croton zambesicus, ent-18-hydroxy-trachyloban-3-one (DT6), and a synthetic diterpene of similar structure, ent-trachyloban-14,15-dione (DT10) in rat aorta. DT6 and DT10 inhibited aorta contraction in a concentration-dependent manner. Both were more potent inhibitors of KCl-evoked contraction than noradrenaline-evoked contraction. Nitric oxide (NO) synthase inhibition did not significantly affect DT6 effect whereas it significantly decreased DT10 inhibitory potency. In fura-2 loaded aorta rings, DT10 simultaneously inhibited KCl-evoked contraction and cytosolic calcium increase in a concentration-dependent manner. Furthermore, DT10 significantly inhibited calcium channel current recorded by the patch-clamp technique in human neuroblastoma cells SH-SY5Y. However, despite potentiation of 8-bromo-cGMP-response, DT6 and DT10 as verapamil depressed acetylcholine-evoked relaxation, DT6 being the most potent, while only DT6 and DT10 depressed SNAP-evoked relaxation. In conclusion, these data suggest that vasorelaxant activity of diterpenes (DT) is associated with the blockade of L-type voltage-operated calcium channels. Inhibition of NO-dependent relaxation by DT could be related to a decrease in NO availability.

The onset temperature of the retro-Diels-Alder reactions of diketo-1,3-dioxin-2-ones to generate alpha,gamma,epsilon-triketo-ketenes was found to be significantly reduced with 2-phenyl substitution. These ketenes, generated at 78 degrees C, were trapped with alcohols to provide resorcylate esters following aromatization by sequential reaction with cesium acetate and trifluoroacetic acid. The methodology was applied iteratively to the total synthesis of the resorcylate antibiotics W1278A, -B, and -C. It is noteworthy that in this process the linking of the monomer units occurs during construction of the aromatic ring.

A diastereoselective approach to polyoxygenated atisene-type diterpenes starting from (S)-(+)-carvone is described. The key steps used in the preparation of the atisene framework are an intramolecular Diels–Alder reaction, an intramolecular diazoketone cyclopropanation, an endocyclic cyclopropane ring cleavage and the regioselective reduction of an allylic bromide by a low-valent chromium species. The synthesis of natural atisanes antiquorin (1), atis-16-ene-3,14-dione (3), atis-16-ene-2,3,14-trione (8) and 3β-hydroxy-atis-16-ene-2,14-dione (9) following this approach is presented. Also described is the synthesis of 18-hydroxy-atis-16-ene-3,14-dione (5), the structure erroneously assigned to an atisene isolated from the Fijian plant Euphorbia fidjiana. This work shows that the natural atisene isolated from this plant is, in fact, the epimer at C-4 of this compound.

A general synthetic approach to the polycyclic carbon skeleton of biogenetically related trachylobane, beyerane, atisane, and kaurane diterpenes from carvone is described. The skeleton of these diterpenes is prepared from a common intermediate, that is, 25, readily prepared from carvone using an IMDA reaction and an intramolecular diazo ketone cyclopropanation of an unsaturated ketone as key steps. The tetracyclic diterpene ring systems are obtained from this key trachylobane-type intermediate through the regioselective reductive cleavage of the cyclopropane ring, after adequate modification of the functionalization around the tricyclo[3.2.1.02,7]octane moiety.

A new stereoselective approach to polyoxygenated atisane-type diterpenes starting from (S)-(+)-carvone is described. The key steps involve an intramolecular Diels–Alder reaction, an unusual intramolecular diazo ketone cyclopropanation of an unsaturated ketone, and a regioselective endocyclic cleavage of a cyclopropyl carbinyl radical as key synthetic steps. The synthesis of the bioactive polyoxygenated atisanes atis-16(17)-en-3,14-dione ( 2 ) and 3R-hydroxy-atis-16(17)-en-2,14-dione ( 3 ) following this approach is presented.

Studies about the sex pheromone of the mealybug Dysmicoccus grassii , a main pest of Canary Islands banana cultivars, showed strong evidence that (-)-(R)-lavandulyl propionate and acetate in a 6:1 ratio are principal components of it. Volatile collection and GC-MS analysis from aeration of virgin females allowed the structural elucidation of the compounds. The activity and stereochemistry of both substances were established by means of relative attraction of mealybug males to synthetic standards in competitive Petri dish bioassays. (R)-Lavandulyl propionate induced a stronger attractive effect when compared to (R)-lavandulyl acetate. The attractiveness of the mixture of the two compounds at the original source ratio showed no statistically significant difference from that of the sum of each of the single compounds alone, suggesting that both components are not synergistic but additive.

Diketo-1,3-dioxin-2-ones underwent retro-Diels-Alder reaction on heating in toluene at 110 degrees C to generate alpha,gamma,-triketo-ketenes. These were trapped with alcohols to provide 2,4,6-triketocarboxylates, which were smoothly aromatized by sequential reaction with potassium carbonate and methanolic hydrogen chloride to give resorcylate esters. The reaction was applied in the total synthesis of the marine antifungal agents 15G256beta (1), 15G256iota (2), and 15G256pi (3) and the mycotoxin S-(-)-zearalenone (4).

The diterpenes previously isolated from the leaves of Croton zambesicus were tested to evaluate their vasorelaxant activity on the Wistar rat aorta. Their vasorelaxant effect was compared to a series of synthetic trachylobanes and related polycyclic compounds on KCl- or noradrenaline-induced contractions in order to evaluate structure-activity relationships. We demonstrate the vasorelaxant properties of some pure trachylobane diterpenes at low concentration (IC50 < 10 microM) on KCl-induced contractions, but none have a significant effect in noradrenaline-induced contractions. Comparing structures and activity we observed that a C-14 carbonyl group associated with a C-15 hydroxy or ketone function or a C-3 carbonyl associated with a hydroxymethyl group plays an important role in the vasorelaxant activity of trachylobane diterpenes. We also observed that the absolute configuration or the cleavage of the C13-C16 cyclopropane bond does not have a marked effect on the activity. The cytotoxicity of all of these compounds has also been evaluated on HeLa cells in order to verify that the vasorelaxant activity was not correlated with general cytotoxicity.

The transformation of alkyl halides into alcohols via a two-step process based on the reaction with DMF catalyzed by Ag(I) salts followed by acid or basic hydrolysis of the intermediate formate ester has been evaluated. The results show that a large variety of primary and some secondary alkyl halides can be transformed efficiently into the corresponding alcohols, making this alkyl halide to alcohol interconversion a valuable alternative to the existing procedures, particularly in molecules with labile functional groups that are generally involved in multistep synthesis.

The commercially available monoterpene carvone has been efficiently converted into the tricyclo[3.2.1.0 2.7 ]octane and bicyclo[3.2.1]octane systems characteristic of some biologically active compounds. The sequence used for this transformation involves as key features an intramolecular Diels-Alder reaction of a 5-vinyl-1,3-cyclohexadiene and a cyclopropane ring opening. Keywords: Carvone, Diels-Alder reaction, cyclopropane cleavage, 5-vinyl-1,3-cyclohexadiene, samarium diiodide, bicyclo[3.2.1]octane, tricyclo[3.2.1.0 2.7 ]octane Introduction The bicyclo[3.2.1]octane ring system is the basic framework of many important biologically active natural compounds, particularly tri- and tetracyclic sesqui- and diterpenes [1]. The widespread occurrence of this common structural motif in so many biologically active natural products has stimulated the preparation of simple non-natural structures containing the carbo-bicyclic system with variable functional diversity, many of which have also shown relevant biological activity. A logical consequence of the interest in this type of compounds has been the development of a plethora of synthetic methods for making bicyclo[3.2.1]octanes [2], in many cases appropriately functionalised to be useful intermediates in the synthesis of the more complex natural products containing this bicyclic

The X-ray structure of di­methyl (Z)-[(8aS,2R,4aR,4bR)-8a-methoxy­carbonyl-1,4a,7-tri­methyl-8-oxo-2,3,4,4a,4b,5,8,8a,9,10-deca­hydro­phenanthren-2-yl]-2-butenedioate, C25H32O7, confirmed its relative configuration. The structure shows the bend in the molecular skeleton as found for similar compounds. Weak intermolecular C—H⋯O interactions have been found in the crystal.

Polycyclic terpenoid compounds with a methylcyclohexene moiety at the A-ring, such as 1 and 7, give a regio- and stereoselective ene reaction when heated at low temperatures with dimethyl acetylenedicarboxylate. The structure and stereochemistry of the compound formed in the case of 1, e.g. 5, is determined by X-ray analysis.