Complexes of copper(II) with 3-(ortho-substituted phenylhydrazo)pentane-2,4-diones: syntheses,properties and catalytic activity for cyclohexane oxidation

Reactions of copper(II) with 3-phenylhydrazopentane-2,4-diones X-2-C6H4-NHN = C{C(= O)CH3}(2) bearing a substituent in the ortho-position [X = OH (H2L1) 1, AsO3H2 (H3L2) 2, Cl (HL3) 3, SO3H (H2L4) 4, COOCH3 (HL5) 5, COOH (H2L6) 6, NO2 (HL7) 7 or H (HL8) 8] lead to a variety of complexes including the monomeric [CuL4(H2O)(2)]center dot H2O 10, [CuL4(H2O)(2)] 11 and [Cu(HL4)(2)(H2O)(4)] 12, the dimeric [Cu-2(H2O)(2)(mu-HL2)(2)] 9 and the polymeric [Cu(mu-L-6)](n)] 13 ones, often bearing two fused six-membered metallacycles. Complexes 10-12 can interconvert, depending on pH and temperature, whereas the Cu(II) reactions with 4 in the presence of cyanoguanidine or imidazole (im) afford the monomeric compound [Cu(H2O)(4){NCNC(NH2)(2)}(2)](HL4)(2)center dot 6H(2)O 14 and the heteroligand polymer [Cu(mu-L-4)(im)](n) 15, respectively. The compounds were characterized by single crystal X-ray diffraction (complexes), electrochemical and thermogravimetric studies, as well as elemental analysis, IR, H-1 and C-13 NMR spectroscopies (diones) and ESI-MS. The effects of the substituents in 1-8 on the HOMO-LUMO gap and the relative stability of the model compounds [Cu(OH)(L-8)(H2O)]center dot H2O, [Cu(L-1)(H2O)(2)]center dot H2O and [Cu(L-4)(H2O)(2)]center dot H2O are discussed on the basis of DFT calculations that show the stabilization follows the order: two fused 6-membered > two fused 6-membered/5-membered > one 6-membered metallacycles. Complexes 9, 10, 12 and 13 act as catalyst precursors for the peroxidative oxidation (with H2O2) of cyclohexane to cyclohexanol and cyclohexanone, in MeCN/H2O (total yields of ca. 20% with TONs up to 566), under mild conditions

Biofortified Diets Containing Algae and Selenised Yeast: Effects on Growth Performance, Nutrient Utilization, and Tissue Composition of Gilthead Seabream (Sparus aurata)

Efforts have been made to find natural, highly nutritious alternatives to replace fish meal (FM) and fish oil (FO), which can simultaneously promote fish health and improve the nutritional quality of filets for human consumption. This study evaluated the impact of biofortified diets containing microalgae (as replacement for FM and FO), macroalgae (as natural source of iodine) and selenised yeast (organic source of selenium) on gilthead seabream growth, nutrient utilization, tissue composition and gene expression. A control diet (CTRL) with 15% FM and 5.5% FO was compared with three experimental diets (AD1, AD2, and AD3), where a microalgae blend (Chlorella sp., Tetraselmis sp., and DHA-rich Schizochytrium sp.) replaced 33% of FM. Diet AD1 contained 20% less FO. Diets were supplemented with Laminaria digitata (0.4% AD1 and AD2; 0.8% AD3) and selenised yeast (0.02% AD1 and AD2; 0.04% AD3). After feeding the experimental diets for 12 weeks, growth was similar in fish fed AD1, AD2, and CTRL, indicating that microalgae meal can partially replace both FM and FO in diets for seabream. But AD3 suppressed fish growth, suggesting that L. digitata and selenised yeast supplementation should be kept under 0.8 and 0.04%, respectively. Despite lower lipid intake and decreased PUFAs bioavailability in fish fed AD3, compared to CTRL, hepatic elovl5 was upregulated resulting in a significant increase of muscle EPA + DHA. Indeed, filets of fish fed AD2 and AD3 provided the highest EPA + DHA contents (0.7 g 100 g–1), that are well above the minimum recommended values for human consumption. Fish consuming the AD diets had a higher retention and gain of selenium, while iodine gain remained similar among diets. Upregulation of selenoproteins (gpx1, selk, and dio2) was observed in liver of fish fed AD1, but diets had limited impact on fish antioxidant status. Overall, results indicate that the tested microalgae are good sources of protein and lipids, with their LC-PUFAs being effectively accumulated in seabream muscle. Selenised yeast is a good fortification vehicle to increase selenium levels in fish, but efforts should be placed to find new strategies to fortify fish in iodineThis work has received funding from the European Union’s Horizon 2020 Research and Innovation Programe under Grant Agreement No. 773400 (SEAFOODTOMORROW) and from the project ATLANTIDA (ref. NORTE-01-0145-FEDER-000040), supported by the Norte Portugal Regional Operational Programme (NORTE 2020), under the PORTUGAL 2020 Partnership Agreement and through the European Regional Development Fund (ERDF). This work received financial support from REQUIMTE/LAQV national funds (FCT) through project UID/QUI/50006/2019. LV acknowledges national funds provided by FCT to CIIMAR (UIDB/04423/2020 and UIDP/04423/2020), PP-F acknowledges MAR2020 national funds provided to IPMA (DIVERISAQUA project - 16-02-01-FEAM-66) and MF acknowledges FCT for the grant SFRH/BD/144843/2019.info:eu-repo/semantics/publishedVersio

Population genomics of Bombus terrestris reveals high but unstructured genetic diversity in a potential glacial refugium

Ongoing climate change is expected to cause an increase in temperature and a reduction of precipitation levels in the Mediterranean region, which might cause changes in many species distributions. These effects negatively influence species gene pools, decreasing genetic variability and adaptive potential. Here, we use mitochondrial DNA and RADseq to analyse population genetic structure and genetic diversity of the bumblebee species Bombus terrestris (subspecies Bombus terrestris lusitanicus), in the Iberian Peninsula. Although this subspecies shows a panmictic pattern of population structure across Iberia and beyond, we found differentiation between subspecies B. t. lusitanicus and B. t. africanus, probably caused by the existence of barriers to gene flow between Iberia and North Africa. Furthermore, the results revealed that the Iberian Peninsula harbours a large fraction of B. terrestris intraspecific genetic variation, with the highest number of mitochondrial haplotypes found when compared with any other region in Europe studied so far, suggesting a potential role for the Iberian Peninsula as a glacial refugium. Our findings strengthen the idea that Iberia is a very important source of diversity for the global genetic pool of this species, because rare alleles might play a role in population resilience against human- or climate-mediated changes.info:eu-repo/semantics/publishedVersio

Useful biometric variables in Iberian exuviae of Boyeria irene (Fonscolombe, 1838) (Odonata: Aeshnidae)

In species of similar shape and size, biometric analyses make it possible to establish differences. Within one species, biometrics can help researchers to detect differences between populations and analyze their adaptations to environmental conditions. Until now little was known about the biometrics of the Iberian populations of Boyeria irene (Odonata: Aeshnidae), a large species living mainly in southern Europe. Eight biometric variables were studied in male and female exuviae of B. irene collected in three rivers of the Iberian Peninsula, with the objective of ascertaining which are the most suitable populations of this species to study. An analysis of principal components (PCA) shows that lengths of the epiproct, paraproct and prementum are the most influential in each of the three populations. The other variables (head width, body length, length of the gonapophyses, maximum and minimum width of the prementum) proved not to be relevant in this context

Photocatalytic ozonation of urban wastewater and surface water using immobilized TiO2 with LEDs: Micropollutants, antibiotic resistance genes and estrogenic activity

Photocatalytic ozonation was employed for the first time in continuous mode with TiO2-coated glass Raschig rings and light emitting diodes (LEDs) to treat urban wastewater as well as surface water collected from the supply area of a drinking water treatment plant (DWTP). Different levels of contamination and types of contaminants were considered in this work, including chemical priority substances (PSs) and contaminants of emerging concern (CECs), as well as potential human opportunistic antibiotic resistant bacteria and their genes (ARB&ARG). Photocatalytic ozonation was more effective than single ozonation (or even than TiO2 catalytic ozonation) in the degradation of typical reaction by-products (such as oxalic acid), and more effective than photocatalysis to remove the parent micropollutants determined in urban wastewater. In fact, only fluoxetine, clarithromycin, erythromycin and 17-alpha-ethinylestradiol (EE2) were detected after photocatalytic ozonation, by using solid-phase extraction (SPE) pre-concentration and LC-MS/MS analysis. In surface water, this treatment allowed the removal of all determined micropollutants to levels below the limit of detection (0.01-0.20 ng L(-1)). The efficiency of this process was then assessed based on the capacity to remove different groups of cultivable microorganisms and housekeeping (16S rRNA) and antibiotic resistance or related genes (intI1, blaTEM, qnrS, sul1). Photocatalytic ozonation was observed to efficiently remove microorganisms and ARGs. Although after storage total heterotrophic and ARB (to ciprofloxacin, gentamicin, meropenem), fungi, and the genes 16S rRNA and intI1, increased to values close to the pre-treatment levels, the ARGs (blaTEM, qnrS and sul1) were reduced to levels below/close to the quantification limit even after 3-days storage of treated surface water or wastewater. Yeast estrogen screen (YES), thiazolyl blue tetrazolium reduction (MTT) and lactate dehydrogenase (LDH) assays were also performed before and after photocatalytic ozonation to evaluate the potential estrogenic activity, the cellular metabolic activity and the cell viability. Compounds with estrogenic effects and significant differences concerning cell viability were not observed in any case. A slight cytotoxicity was only detected for Caco-2 and hCMEC/D3 cell lines after treatment of the urban wastewater, but not for L929 fibroblasts.info:eu-repo/semantics/acceptedVersio

Geographical variation of prementum size in Iberian Cordulegaster boltonii (Odonata: Cordulegastridae) populations

Within wide geographical areas, Odonata populations can show biometric differences as a consequence of both biotic (e.g., predation, competition) and abiotic factors (mainly temperature). These differences can occur in the larval stage, although reliable characters are needed to detect differences. We analyzed whether Cordulegaster boltonii larvae from 18 Iberian populations differ regarding head width and prementum size (maximum width, minimum width, and maximum length), using measurements taken on final stage exuviae. Prementum length was greater in southern populations than in northern ones. Geographic latitude and temperature were the variables that best explained this variation in females, whereas latitude and altitude above sea level offered the best explanation among males

Hunt for new phenomena using large jet multiplicities and missing transverse momentum with ATLAS in 4.7 fb−1 of s√=7TeV proton-proton collisions

Results are presented of a search for new particles decaying to large numbers of jets in association with missing transverse momentum, using 4.7 fb−1 of pp collision data at s√=7TeV collected by the ATLAS experiment at the Large Hadron Collider in 2011. The event selection requires missing transverse momentum, no isolated electrons or muons, and from ≥6 to ≥9 jets. No evidence is found for physics beyond the Standard Model. The results are interpreted in the context of a MSUGRA/CMSSM supersymmetric model, where, for large universal scalar mass m 0, gluino masses smaller than 840 GeV are excluded at the 95% confidence level, extending previously published limits. Within a simplified model containing only a gluino octet and a neutralino, gluino masses smaller than 870 GeV are similarly excluded for neutralino masses below 100 GeV