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Several pathogens are known to be transmitted by arthropods. One of the most relevant, in economic terms, affecting animals is bluetongue virus. Its known vectors are several species of Culicoides midges. In Europe, the considered main vector species are Culicoides imicola and Culicoides obsoletus, though other species may be implicated at different levels. In the present work, the activity of these vector species between sunset and sunrise from May to November is analyzed according to their captures in a rotator bottle collector adapted to a light trap. Additionally, the Culicoides populations of two areas in Mallorca (Spain) with different characteristics (rural vs. urban) are compared. The results indicated that June is the month of higher abundance of C. obsoletus in our climatic conditions—being active during the first three hours after sunset. Conversely, C. imicola reached the maximum level of captures during October, and captures were more evenly distributed during the night. Collections from the two areas revealed that Culicoides populations were composed by the same species; however, abundance and sex ratio presented marked differences. These results add valuable insight into the ecology of Culicoides and may be used to design more accurate strategies to control diseases associated with Culicoides.

Phlebotomine sand flies are vectors of several diseases of importance for public health, including leishmaniosis, bartonellosis, and sand fly fevers. An entomological survey on blood-feeding Diptera was conducted in June–November 2020–2021 to know the diversity of insect vectors in Mallorca (Balearic Islands, Spain). Among the vectors collected, Phlebotomus (Larroussius) perfiliewi Parrot, 1930 was found being the first record of this species in Spain. Phlebotomus perfiliewi s.l. is one of the main vectors of Leishmania infantum in the Mediterranean Basin and Central Asia. The identification of this species was confirmed by both morphological features and DNA barcoding. Phylogenetic analyses showed that the specimens captured were Ph. perfiliewi s.s. (99.85–100% homologues from Italy and Algeria specimens), with a sequence divergence of 0.17%. The cytochrome c oxidase subunit I gene clearly separates the three species that make up the Ph. perfiliewi species complex. In addition, we also provide a brief discussion about their identification remarks, phylogenetic relationships, and vector status.

Mitochondria-targeting drugs and diagnostics are used in the monitoring and treatment of mitochondrial pathologies. In this respect, a great number of functional compounds have been made mitotropic by covalently attaching the active moiety onto a triphenylphosphonium (TPP) cation. Among these compounds, a number of molecular detectors for reactive oxygen species (ROS) are based on fluorescent and chemiluminescent probes. In this regard, luminol (probably the most widely known chemiluminescent molecule) has been employed for a number of biological applications, including ROS detection. Its oxidation under specific conditions triggers a cascade of reactions, ultimately leading to the excited 3-aminophthalate (3AP *), which emits light upon deactivation. Hence, the photophysical interaction between the light-emitting species 3AP * and TPP cations needs to be evaluated, as it can add valuable information on the design of novel emission-based mitotropic systems. We herein investigate the quenching effect of ethyltriphenylphosphonium cation onto substituted 3-aminophthalates. These were prepared in situ upon hydrolysis of the corresponding anhydrides, which were synthesized from 3-aminophthalimides. Steady-state fluorescence and time-resolved experiments were employed for the evaluation of a possible electron transfer quenching by phosphonium ions. Our experimental results confirmed such quenching, suggesting it is mainly dynamic in nature. A minor contribution of static quenching that was also detected is attributed to complex formation in the ground state. Accordingly, the chemiluminescence of luminol was indeed strongly reduced in the presence of phosphonium ions. Our results have to be taken into account during the design of new chemiluminescent mitotropic drugs or diagnostic agents of the luminol family.

Photocycloreversion plays a central role in the study of the repair of DNA lesions, reverting them into the original pyrimidine nucleobases. Particularly, among the proposed mechanisms for the repair of DNA (6-4) photoproducts by photolyases, it has been suggested that it takes place through an intermediate characterized by a four-membered heterocyclic oxetane or azetidine ring, whose opening requires the reduction of the fused nucleobases. The specific role of this electron transfer step and its impact on the ring opening energetics remain to be understood. These processes are studied herein by means of quantum-chemical calculations on the two azetidine stereoisomers obtained from photocycloaddition between 6-azauracil and cyclohexene. First, we analyze the efficiency of the electron-transfer processes by computing the redox properties of the azetidine isomers as well as those of a series of aromatic photosensitizers acting as photoreductants and photo-oxidants. We find certain stereodifferentiation favoring oxidation of the cis-isomer, in agreement with previous experimental data. Second, we determine the reaction profiles of the ring-opening mechanism of the cationic, neutral, and anionic systems and assess their feasibility based on their energy barrier heights and the stability of the reactants and products. Results show that oxidation largely decreases the ring-opening energy barrier for both stereoisomers, even though the process is forecast as too slow to be competitive. Conversely, one-electron reduction dramatically facilitates the ring opening of the azetidine heterocycle. Considering the overall quantum-chemistry findings, N,N-dimethylaniline is proposed as an efficient photosensitizer to trigger the photoinduced cycloreversion of the DNA lesion model.

Four silver phosphate-based materials were successfully synthesized, characterized, and evaluated, together with TiO2, in the photodegradation of synthetic dyes (tartrazine, Orange II, rhodamine, and Brilliant Blue FCF) under two irradiation sources centered at 420 and 450 nm. Scanning Electron Microscopy (SEM) images showed different topologies of the synthesized materials, whereas diffuse reflectance spectra demonstrated that they display absorption up to 500 nm. Degradation experiments were performed in parallel with the silver materials and TiO2. Upon irradiation centered at 420 nm, the abatement of the dyes was slightly more efficient in the case of TiO2—except for Orange II. Nevertheless, upon irradiation centered at 450 nm, TiO2 demonstrated complete inefficiency and silver phosphates accomplished the complete abatement of the dyes—except for Brilliant Blue FCF. A careful analysis of the achieved degradation of dyes revealed that the main reaction mechanism involves electron transfer to the photogenerated holes in the valence band of silver photocatalysts, together with the direct excitation of dyes and the subsequent formation of reactive species. The performance of TiO2 was only comparable at the shorter wavelength when hydroxyl radicals could be formed; however, it could not compete under irradiation at 450 nm since the formed superoxide anion is not as reactive as hydroxyl radicals.

A Decision Support System (DSS) was developed and evaluated to control the Mediterranean fruit fly (medfly), Ceratitis capitata (Wiedermann), by incorporating a semi-automatic pest monitoring and a precision targeting approach in multi-varietal orchards. The DSS consists of three algorithms. DSS1, based on the degree days calculation, defines when the traps should be deployed in the field initiating the medfly population monitoring. DSS2 defines the areas to be treated and the type of treatment based on the number of adult medfly captures, harvesting time, and phenological stage of the host cultivar. DSS3 defines the spraying procedure considering the technical registration properties of the selected insecticide (e.g., withholding period and efficacy duration time) and weather conditions. The DSS was tested in commercial orchard conditions near Rome, central Italy, with a randomized complete blocks experimental design, comparing DSS-assisted and conventional management. In the DSS-assisted plots, a semi-automatic adult medfly monitoring system was deployed, composed of real-time, wireless electronic traps. The output of the functioning DSS is a map of spraying recommendation, reporting the areas to be treated and the treatment type (bait or cover insecticide spraying). The farmer was left free to follow, or not, the DSS indications. The first medfly captures were observed on June 30, whereas the DD threshold was reached on July 3 when the DSS started to operate. The field test produced 29 DSS decisions from July 3 to September 1 and confirmed that medfly management using the DSS substantially reduced the number of pesticide applications, the treated area, and the volumes of pesticide utilization. No significant differences in infested fruit were observed between DSS-assisted and conventional management. The level of acceptance of the DSS by the farmer was 78%. This evidence confirmed the requirement of fully involving farmers and pest managers during the evaluation process of DSS.

The monitoring of reactive oxygen species in living cells provides valuable information on cell function and performance. Lately, the development of chemiluminescence-based reactive oxygen species monitoring has gained increased attention due to the advantages posed by chemiluminescence, including its rapid measurement and high sensitivity. In this respect, specific organelle-targeting trackers with strong chemiluminescence performance are of high importance. We herein report the synthesis and chemiluminescence properties of eight novel phosphonium-functionalized amino-acylated luminol and isoluminol derivatives, designed as mitochondriotropic chemiluminescence reactive oxygen species trackers. Three different phosphonium cationic moieties were employed (phenyl, p-tolyl, and cyclohexyl), as well as two alkanoyl chains (hexanoyl and undecanoyl) as bridges/linkers. Synthesis is accomplished via the acylation of the corresponding phthalimides, as phthalhydrazide precursors, followed by hydrazinolysis. This method was chosen because the direct acylation of (iso)luminol was discouraging. The new derivatives’ chemiluminescence was evaluated and compared with that of the parent molecules. A relatively poor chemiluminescence performance was observed for all derivatives, with the isoluminol-based ones being the poorest. This result is mainly attributed to the low yield of the fluorescence species formation during the chemiluminescence oxidation reaction.

Reactive oxygen species (ROS) can provoke damage to cells, where their concentrations are regulated by antioxidants. As the hydroxyl radical (•OH) is the most oxidizing ROS, we have focused our attention on the use of a mechanistically based time-resolved methodology, such as laser flash photolysis, to determine the relative reactivity of alcoholic beverages towards •OH as an indicator of their antioxidant potential. The selected drinks were of two different origins: (i) those derived from grapes such as red wine, white wine, white vermouth, marc and brandy and (ii) spirits not derived from grapes: triple sec, gin, whisky, and rum. Initially, we determined the quenching rate constant of ethanol with •OH and then we explored the reactivity of the different beverages, which was higher than expected based on their alcoholic content. This can be attributed to the presence of antioxidants and was especially remarkable for the grape-derived drinks.

Glioblastoma (GBM) is the most common and aggressive of all brain tumors, with a median survival of only 14 months after initial diagnosis. Novel therapeutic approaches are an unmet need for GBM treatment. MicroRNAs (miRNAs) are a class of small non-coding RNAs that regulate gene expression at the post-transcriptional level. Several dysregulated miRNAs have been identified in all cancer types including GBM. In this study, we aimed to uncover the role of miR-143 in GBM cell lines, patient samples, and mouse models. Quantitative real-time RT-PCR of RNA extracted from formalin-fixed paraffin-embedded (FFPE) samples showed that the relative expression of miR-143 was higher in GBM patients compared to control individuals. Transient transfection of GBM cells with a miR-143 oligonucleotide inhibitor (miR-143-inh) resulted in reduced cell proliferation, increased apoptosis, and cell cycle arrest. SLC30A8, a glucose metabolism-related protein, was identified as a direct target of miR-143 in GBM cells. Moreover, multiple injections of GBM tumor-bearing mice with a miR-143-inh-liposomal formulation significantly reduced tumor growth compared to control mice. The reduced in vitro cell growth and in vivo tumor growth following miRNA-143 inhibition suggests that miR-143 is a potential therapeutic target for GBM therapy.

Two new 2-(2´-hydroxyaryl)benzotriazole derivatives were synthesized and studied by photophysical and photochemical techniques in order to assess their ability to act as UV-filters. The absorption and emission properties of both compounds were determined in solvents of different polarity. In non polar solvent, a photoinduced excited state intramolecular proton transfer was established leading to efficient non radiative dissipation of UV-energy. In addition, the compounds considered were photostable under irradiation with simulated sunlight.

Photosensitization by drugs is a problem of increasing importance in modern life. This phenomenon occurs when a chemical substance in the skin is exposed to sunlight. Photosensitizing drugs are reported to cause severe skin dermatitis, and indeed, it is generally advised to avoid sunbathing and to apply sunscreen. In this context, the nonsteroidal anti-inflammatory drug (NSAID) diclofenac is a photosensitive drug, especially when administered in topical form. In this work, efforts have been made to design and study an innovative pro-drug/pro-filter system containing diclofenac and the UVA filter avobenzone in order to develop a safer use of this topical drug. The design is based on the presence of a well-established photoremovable phenacyl group in the avobenzone structure. Steady-state photolysis of the dyad in hydrogen-donor solvents, monitored by UV-Vis spectrophotometry and HPLC, confirms the simultaneous photorelease of diclofenac and avobenzone. Laser flash photolysis and phosphorescence emission experiments allow us to gain insight into the photoactive triplet excited-state properties of the dyad. Finally, it is shown that avobenzone provides partial photoprotection to diclofenac from photocyclization to carbazole derivatives.

Electron transfer involving nucleic acids and their derivatives is an important field in bioorganic chemistry, specifically in connection with its role in the photo-driven DNA damage and repair. Four-membered ring heterocyclic oxetanes and azetidines have been claimed to be the intermediates involved in the repair of DNA (6-4) photoproduct by photolyase. In this context, we examine here the redox properties of the two azetidine isomers obtained from photocycloaddition between 6-aza-1,3-dimethyluracil and cyclohexene. Steady-state and time-resolved fluorescence experiments using a series of photoreductants and photooxidants have been run to evaluate the efficiency of the electron transfer process. Analysis of the obtained quenching kinetics shows that the azetidine compounds can act as electron donors. Additionally, it appears that the cis isomer is more easily oxidized than its trans counterpart. This result is in agreement with electrochemical studies performed on both azetidine derivatives.

Worldwide, pyrethroids are one of the most widely used insecticide classes. In addition to serving as personal protection products, they are also a key line of defence in integrated vector management programmes. Many studies have assessed the effects of sublethal pyrethroid doses on mosquito fitness and behaviour. However, much remains unknown about the biological, physiological, demographic, and behavioural effects on individual mosquitoes or mosquito populations when exposure occurs via spatial treatments. Here, females and males of two laboratory-reared mosquito species, Culex pipiens and Aedes albopictus, were exposed to five different treatments: three doses of the pyrethroid prallethrin, as well as an untreated and a negative control. The effects of each treatment on mosquito species, sex, adult mortality, fertility, F1 population size, and biting behaviour were also evaluated. To compare knockdown and mortality among treatments, Mantel–Cox log-rank tests were used. The results showed that sublethal doses reduced mosquito survival, influencing population size in the next generation. They also provided 100% protection to human hosts and presented relatively low risks to human and environmental health. These findings emphasise the need for additional studies that assess the benefits of using sublethal doses as part of mosquito management strategies.

Modern agriculture requires technology to give precise measures about relevant parameters such as pest control. Here, we developed a decision support system (DSS) based on semi-automatic pest monitoring for managing the olive fruit fly Bactrocera oleae (Rossi), in Mallorca (Balearic Islands, Spain). The DSS was based on an algorithm that took into account spatial and temporal patterns of olive fruit fly population in an orchard where all trees were georeferenced, thus precise treatments against the pest were conducted through a location aware system (LAS). The olive fruit fly adult population was monitored by using ad hoc off-the-grid autonomous electronic traps.The results were compared with those obtained with conventional methods. For a pilot trial, we selected an olive-producing orchard, where from June to October 2015, three plots using LAS management and three plots under conventional control (NO-LAS plots) were compared. Spray threshold considered both adult population and fruit damage. An additional non-sprayed plot was selected for assessing biological control due to the parasitoid, Psyttalia concolor (Szépligeti). Results showed that the use of DSS reduced by 36.84% the volume of insecticide used in LAS compared to NO-LAS plots. Accordingly, time and distance needed for spraying were also reduced. Adult olive fruit fly population was lower in the LAS plots when compared with the NO-LAS plots; conversely, fruit infestation was higher in LAS compared with NO-LAS. The implementation of LAS and DSS at field level allowed real-time monitoring of adult olive flies, thereby increasing the accuracy and precision of sprays in time and space and decreasing impact on natural enemies.

The Ethiopian fruit fly (EFF), Dacus ciliatus, is a key, invasive pest of melons in the Middle East. We developed and implemented a novel decision support system (DSS) to manage this pest in a greenhouse environment in Southern Israel. Dacus ciliatus is commonly controlled in Israel with repeated calendar-sprayings (every 15 days) of pyrethroid pesticides. The current study compares the performance of a DSS against calendar-spraying management (CSM). DSS was based on EFF population monitoring and infestation. DSS took into consideration concerns and observations of expert managers and farmers. During 2014, EFF damage was concentrated in the spring melon production season. Fall and winter production did not show important damage. Damage during the spring of 2014 started to increase when average EFF/trap/day reached 0.3. This value was suggested as the threshold to implement pesticide spraying in DSS greenhouses. EFF/trap/day trends were derived from monitoring with conventional traps and a novel electronic remote sensing trap, developed by our group. CSM during the spring of 2015 included 3 EFF control sprays, while DSS-managed greenhouses were only sprayed once. At the end of the spring season, damage was slightly higher in DSS greenhouses (1.5%), but not significantly different to that found in CSM greenhouses (0.5%). Results support continuing DSS research and optimization to reduce/remove pesticide use against EFF in melon greenhouses. Interactions with farmers and managers is suggested as essential to increase adoption of DSS in agriculture.