Elicitor-Induced VOC Emission by Grapevine Leaves: Characterisation in the Vineyard

The present study is aimed at determining whether leaf volatile organic compounds (VOCs) are good markers of the grapevine response to defence elicitors in the field. It was carried out in two distinct French vineyards (Burgundy and Bordeaux) over 3 years. The commercial elicitor Bastid^® (Syngenta, Saint-Sauveur, France) (COS-OGA) was first used to optimise the VOCs’ capture in the field; by bagging stems together with a stir bar sorptive extraction (SBSE) sensor. Three elicitors (Bastid^®, copper sulphate and methyl jasmonate) were assessed at three phenological stages of the grapevines by monitoring stilbene phytoalexins and VOCs. Stilbene production was low and variable between treatments and phenological stages. VOCs—particularly terpenes—were induced by all elicitors. However, the response profiles depended on the type of elicitor, the phenological stage and the vineyard, and no sole common VOC was found. The levels of VOC emissions discriminated between weak (Bastid^® and copper sulphate) and strong (methyl jasmonate) inducers. Ocimene isomers were constitutively present in the overall blends of the vineyards and increased by the elicitors’ treatments, whilst other VOCs were newly released throughout the growing seasons. Nonetheless, the plant development and climate factors undoubtedly influenced the release and profiles of the leaf VOCs.     

Poly(ε-caprolactone)-Based Graft Copolymers: Synthesis Methods and Applications in the Biomedical Field: A Review

Synthetic biopolymers are attractive alternatives to biobased polymers, especially because they rarely induce an immune response in a living organism. Poly ε-caprolactone (PCL) is a well-known synthetic aliphatic polyester universally used for many applications, including biomedical and environmental ones. Unlike poly lactic acid (PLA), PCL has no chiral atoms, and it is impossible to play with the stereochemistry to modify its properties. To expand the range of applications for PCL, researchers have investigated the possibility of grafting polymer chains onto the PCL backbone. As the PCL backbone is not functionalized, it must be first functionalized in order to be able to graft reactive groups onto the PCL chain. These reactive groups will then allow the grafting of new reagents and especially new polymer chains. Grafting of polymer chains is mainly carried out by “grafting from” or “grafting onto” methods. In this review we describe the main structures of the graft copolymers produced, their different synthesis methods, and their main characteristics and applications, mainly in the biomedical field.     

Methods for Elemental Analysis of Size-Resolved PM Samples Collected on Aluminium Foils: Results of an Intercomparison Exercise

Aluminium is the most common substrate in studies using impactors for the measurement of the number or the weight of size-segregated atmospheric particulate matter (PM), as its characteristics perfectly fit impactor requirements. However, its use is not recommended by manufacturers when one of the purposes of the study is the determination of the metal content in the sample. The aim of this work was to develop an efficient analytical procedure for the removal and acid digestion of PM samples collected on aluminium foils by a cascade impactor to perform the determination of metals. The possibility of performing the trace metal analysis of PM samples collected using aluminium foils is of great importance, as it allows the determination of an accurate size distribution and the elemental composition of the PM collected on each impactor stage. Two procedures were optimised by using different digestion and analysis techniques. Both procedures were then applied to the two halves of several Dekati low-pressure impactor (DLPI) samples, and the results were critically compared. The two procedures proved to be effective in the determination of extremely low concentrations of a large suite of analytes in different size fractions of PM emitted by a brake system.     

Chemical Approach to the Optimization of Conditions Using HS-SPME/GC–MS for Characterization of Volatile Compounds in Eugenia brasiliensis Fruit

Grumixama (Eugenia brasiliensis Lam.) is a native fruit of the Brazilian Atlantic Forest, belonging to the Myrtaceae family, which designatesthe most significant number of species with food potential. It stands out due to its phytochemical characteristics because of the presence of polyphenols and volatile organic compounds. Volatile compounds are substances released by foods that give off an aroma and influence flavor. Solid-phase microextraction is a technique that allows for low-cost, fast, and solvent-free extraction, has an affinity for numerous analytes, and is easily coupled to gas chromatography. The objectives of this work were to evaluate the efficiency of different fibers of SPME (solid-phase microextraction) in the extraction of volatile organic compounds from grumixama pulp; optimize a method for extraction time, temperature, and sample weight; and to determine the characteristic volatile profile of this fruit. For the extraction of volatile compounds, three fibers of different polarities were used: polar polyacrylate (PA) fibers, divinylbenzene/carboxyne/polydimethylsiloxane (DVB/CAR/PDMS) semipolar fibers, and polydimethylsiloxane/divinylbenzene (PDMS/DVB). Fourteen volatile organic compounds (VOCs) were identified by DVB/CAR/PDMS, six by PA, and seven by PDMS/DVB through solid-phase microextraction in the headspace mode (SPME-HS). Considering the total number of compounds identified, regardless of the fiber used, and the optimization of the method, Eugenia brasiliensis presented sesquiterpene fractions (85.7%, 83.3%, and 85.7% of total VOCs) higher than the monoterpene fractions (14.3%, 16.7%, and 14.3%) for DVB/CAR/PDMS, PA, and PDMS/DVB, respectively in its composition. In addition, it was possible to verify that the fiber DVB/CAR/PDMS presented a better efficiency due to the larger chromatographic area observed when the grumixama pulp was subjected to conditions of 75 °C, 2.0 g, and an adsorption time of 20 min.     

Re-Analysis of Abdominal Gland Volatilome Secretions of the African Weaver Ant,Oecophylla longinoda (Hymenoptera: Formicidae)

The African weaver ant, Oecophylla longinoda, is used as a biological control agent for the management of pests. The ant has several exocrine glands in the abdomen, including Dufour’s, poison, rectal, and sternal glands, which are associated with pheromone secretions for intra-specific communication. Previous studies have analyzed the gland secretions of Dufour’s and poison glands. The chemistry of the rectal and sternal glands is unknown. We re-analyzed the secretions from Dufour’s and poison glands plus the rectal and sternal glands to compare their chemistries and identify additional components. We used the solid-phase microextraction (SPME) technique to collect gland headspace volatiles and solvent extraction for the secretions. Coupled gas chromatography–mass spectrometry (GC-MS) analysis detected a total of 78 components, of which 62 were being reported for the first time. These additional components included 32 hydrocarbons, 12 carboxylic acids, 5 aldehydes, 3 alcohols, 2 ketones, 4 terpenes, 3 sterols, and 1 benzenoid. The chemistry of Dufour’s and poison glands showed a strong overlap and was distinct from that of the rectal and sternal glands. The different gland mixtures may contribute to the different physiological and behavioral functions in this ant species.     

On the Effect of the Various Assumptions and Approximations used in Molecular Simulations on the Properties of Bio-Molecular Systems: Overview and Perspective on Issues

Computer simulations of molecular systems enable structure-energy-function relationships of molecular processes to be described at the sub-atomic, atomic, supra-atomic or supra-molecular level and plays an increasingly important role in chemistry, biology and physics. To interpret the results of such simulations appropriately, the degree of uncertainty and potential errors affecting the calculated properties must be considered. Uncertainty and errors arise from (1) assumptions underlying the molecular model, force field and simulation algorithms, (2) approximations implicit in the interatomic interaction function (force field), or when integrating the equations of motion, (3) the chosen values of the parameters that determine the accuracy of the approximations used, and (4) the nature of the system and the property of interest. In this overview, advantages and shortcomings of assumptions and approximations commonly used when simulating bio-molecular systems are considered. What the developers of bio-molecular force fields and simulation software can do to facilitate and broaden research involving bio-molecular simulations is also discussed.     

Unveiling the relevance of the redox character of nitroaromatic and nitroheteroaromatic compounds as potential medicines

This review discusses the state of the art, challenges, and perspectives in recent applications of nitroaromatics and nitroheteroaromatics, which are redox-bio-activated drugs or leads, in Medicinal Chemistry. It deals mainly with the electrochemical approach toward the electron transfer-based molecular mechanisms of drug action, drug design, estimation and measurement of redox potentials, correlation of physicochemical and pharmacological data, and electrochemical studies of the main representatives of nitro-containing prodrugs, along with approaches to combat their toxicity issues, aiming at a better therapeutic profile. Electrochemical investigation plays essential roles, being strategic in the design and discovery of potential medicines.     

Tuning the Regioselective Functionalization of Trifluoromethylated Dienes via Lanthanum-Mediated Single C−F Bond Activation

The development of new fluorine-containing building blocks and their efficient synthetic access is currently a challenging research field. Herein, the highly regio- and stereoselective addition of a large range of aldehydes onto trifluoromethylated benzofulvenes was achieved using a simple La/I₂/DIBAL-Cl system via a selective C−F bond activation process. This versatile methodology provided homodienyl alcohols bearing a terminal CF₂-alkene with potential further applications, as shown by the dehydration to the first benzofulvenes carrying a difluorovinyl group. In addition, for certain electron-poor aldehydes, unprecedented ipso substitution of the CF₃ group in a diene was observed, which, according to DFT studies, is related to the presence of the large, Lewis-acidic lanthanum metal.     

Copper-Photocatalyzed Hydrosilylation of Alkynes and Alkenes under Continuous Flow

Herein, the photocatalytic hydrosilylation of alkynes and alkenes under continuous flow conditions is described. By using 0.2 mol % of the developed [Cu(dmp)(XantphosTEPD)]PF₆ under blue LEDs irradiation, a large panel of alkenes and alkynes was hydrosilylated in good to excellent yields with a large functional group tolerance. The mechanism of the reaction was studied, and a plausible scenario was suggested.     

Controlling Antibacterial Activity Exclusively with Visible Light: Introducing a Tetra-ortho-Chloro-Azobenzene Amino Acid

The introduction of a novel tetra-ortho-chloroazobenzene amino acid (CEBA) has enabled photoswitching of the antimicrobial activity of tyrocidine A analogues by using exclusively visible light, granting spatiotemporal control under benign conditions. Compounds bearing this photoswitchable amino acid become active upon irradiation with red light, but quickly turn-off upon exposure to other visible light wavelengths. Critically, sunlight quickly triggers isomerisation of the red light-activated compounds into their original trans form, offering an ideal platform for self-deactivation upon release into the environment. Linear analogues of tyrocidine A were found to provide the best photocontrol of their antimicrobial activity, leading to compounds active against Acinetobacter baumannii upon isomerisation. Exploration of their N- and C-termini has provided insights into key elements of their structure and has allowed obtaining new antimicrobials displaying excellent strain selectivity and photocontrol.