The importance of trifluoromethyl pyridines in crop protection

The pyridine ring, substituted by a trifluoromethyl substituent has been successfully incorporated into molecules with useful biological properties. During the period 1990 to September 2017, 14 crop protection products bearing a trifluoromethyl pyridine have been commercialized or proposed for an ISO common name, covering fungicides, herbicides, insecticides and nematicides. Chemical processes have been developed to provide trifluoromethyl pyridine intermediates, from non‐fluorinated pyridine starting materials, at scale and with affordable costs of goods. These attractive starting materials were readily adopted by research chemists, and elaborated through simple chemical modifications into new active ingredients. In a second approach, substituted trifluoromethyl pyridine rings have been constructed from acyclic, trifluoromethyl starting materials, which again has served to identify new active ingredients. Molecular matched pair analysis reveals subtle, yet important differences in physicochemical and agronomic properties of trifluoromethyl pyridines compared with the phenyl analogues. This review focuses on the past 27 years, seeking to identify reasons behind the success of such research programmes, and inspire the search for new crop protection chemicals containing the trifluoromethyl pyridine ring. © 2017 Society of Chemical Industry     

Linkage fine-mapping and QTLs affecting morpho-agronomic traits of a Mesoamerican × Andean RIL common bean population

This paper proposes the construction of a genetic linkage map with 376 recombinant inbred lines (RILs) derived from a cross between Mesoamerican?×?Andean common bean (Phaseolus vulgaris L) parents based on single nucleotide polymorphism (SNP) markers; and to detect quantitative trait loci (QTLs) associated with seven morpho-agronomic traits: number of days to flowering (DF), number of days to maturity (DM) or crop cycle; plant architecture (ARC); seed yield (YLD); degree of seed flatness (SF); seed shape (SS); and 100-seed weight (SW). A total of 3060 polymorphic SNP markers were used and 2041 segregated at a 1:1 ratio in the RIL population, as expected. These markers were subjected to linkage analysis in each chromosome. The genetic linkage analysis resulted in linkage maps with a total of 1962 markers spanning 1079.21 cM. A total of 29 QTLs associated with seven morpho-agronomic traits were detected on the 11 chromosomes, which explained between 3.83 and 32.92% of the phenotypic variation in DF. A total of 18 candidate genes associated with the detected QTLs were identified and related with biological processes, molecular functions and cellular components.     

Hydrogeochemistry of the Subaé River Impacted by Lead Smelting Activities,Bahia State,Brazil: Geochemical Characterization and Fluxes of Metals

The Subaé river watershed is considered one of the most critical Pb-impacted environments in Brazil and around the world, due to pollutant dispersion during 33 years of lead ore purification in Santo Amaro da Purification. Severe damages have been reported in biota and population, which depends on the Subaé river watershed quality for agriculture, fishing, and shellfish harvesting. This study aims to understand the geochemical characteristics and dynamics of the river close to the former Pb smelter. The river was sampled at eight sites upstream and eight sites downstream the smelter, near the estuary in the Todos os Santos Bay, six times during a year. Immediate analyses were performed by multiprobe. Major ions were measured by chromatography, dissolved metals by ICP-OES in the filtrated samples (0.45 μm), and particulate metals >?0.45 μm by EDX spectrometry. The ions Na⁺ and HCO₃^? are dominated in the river. Most of the samples (47.6%) were classified as sodic, due to oceanic saline intrusion during tide. Despite the high pollution caused by the smelter from 1960 to 1993, still observed in the surrounding soils, dissolved and particulate metals in the river remained low in all sites during the entire year. Only Cu presented some concentration above the threshold of the Brazilian regulations. The discharge of metals by the river into the Todos os Santos Bay appears to be low for Pb and Zn (2.2 and 14.3 kg km^?1 year^?1, respectively), but higher for Cu comparatively to other worldwide bays.     

Differences in constitutive and inducible defences in pine species determining susceptibility to pinewood nematode

The pinewood nematode, Bursaphelenchus xylophilus, originating from North America (NA), is a major invasive pine pest in Eurasia. It was first detected in Portugal in 1999 associated with maritime pine, Pinus pinaster, and has been differently affecting the main local pine species, P. pinaster and P. pinea. Field studies and direct inoculation experiments in Pinus spp. seedlings, under controlled conditions, were performed to assess whether the differences in constitutive and inducible defences are determining the different susceptibility of pine host species to B. xylophilus. Host co‐evolution with the pathogen was also assessed, including the NA P. radiata, widely used in forestry in the northeast of the Iberian peninsula. Pine mortality in the field was positively related with the abundance of B. xylophilus, and concentration of phenolics and condensed tannins in pines. In the greenhouse assay, seedling tissues were analysed for constitutive investment in defences, as well as the potential inducibility of those defences as driven by B. xylophilus inoculation. Slower growing P. pinea presented higher levels of constitutive defences than faster growing P. pinaster, with only P. pinaster being affected by B. xylophilus. Furthermore, co‐evolution with the pathogen is important, with the fast‐growing NA P. radiata presenting an inducible and effective response to B. xylophilus. Results point to the importance of integrating data on pine life history traits, including growth rate, and production of constitutive and inducible defences, into predictive models for this invasive forest pest.     

Abortion in goats by Caprine alphaherpesvirus 1 in Spain

An abortion outbreak occurred in a goat herd of Murciano‐Granadina breed in Almeria Region in Spain where 80 pregnant females aborted. All bacteriological and parasitological examinations resulted negative, whereas virological investigations and real‐time PCR assay showed the presence of Caprine alphaherpesvirus 1 DNA in the pathological specimens from aborted foetuses. Nucleotide sequence analysis revealed that the DNA was highly close related to the Swiss strain E‐CH (99.7%) and a little less extent to the Italian BA.1 strain (99.4%). Histopathological examination revealed multifocal, well‐circumscribed, 50‐ to 200‐μm‐diameter foci of coagulative necrosis in the liver, lungs and kidneys of three foetuses. In the periphery of the necrosis, there were frequently epithelial cells with the chromatin emarginated by large, round, amphophilic intranuclear viral inclusion bodies. The source of the infection in the herd could not clearly find out even some hypothesis were formulated. This seems to be the first report of an abortion outbreak due to Caprine alphaherpesvirus 1 in a goat herd in Spain.     

Helminthiasis characterization and anthelmintic efficacy for ewes and lambs raised in tropical semiarid region

In this study the helminthiasis and anthelmintic effectiveness in ewes and lambs were evaluated in a semiarid region of Brazil. Twelve sheep farms were investigated using semi-structured questionnaires and fecal egg count (FEC) reduction test was employed to analyze the profile of anthelmintic resistance. Groups of at least 10 animals with FEC ≥ 300 were selected. After 12 h of fasting, homogeneous groups of lambs or ewes were treated with albendazole, levamisole moxidectin, or oxfendazole and control groups were not treated. Feces were collected before treatments and 14 days after, and larvae genera were identified after cuprocultures in both periods. Extensive grazing was the predominant creation system, using hybrid Santa Ines animals. The separation by age was promoted in 75% of herds; however, maternity pickets there were only in three farms. The strategic treatments were performed only in 8.4% of sheep farms and 16.6% used the anthelmintic efficacy test and alternated anthelmintic classes after 1 year. The initial FEC means for lambs were significantly higher than ewe FEC averages. For lamb tests, moxidectin and levamisole showed higher efficacy (p ≤ 0.05) than benzimidazoles. For ewe tests, moxidectin and levamisole showed efficiencies >75%. Haemonchus spp. and Trichostrongylus spp. were the most frequent nematodes before treatments and the genus Haemonchus was the most prevalent after anthelmintic treatments (p < 0.05). Variations of anthelmintic susceptibility were observed for categories and herds evaluated, which emphasizes the importance of the effectiveness tests for the choice of anthelmintics for ewes and lambs.     

Technical note: stearidonic acid metabolism by mixed ruminal microorganisms in vitro

Dietary supplementation of stearidonic acid (SDA; 18:4n-3) has been considered a possible strategy to increase n-3 unsaturated fatty acid content in ruminant products; however, little is known about its metabolism in the rumen. In vitro batch incubations were carried out with bovine ruminal digesta to investigate the metabolism of SDA and its biohydrogenation products. Incubation mixtures (4.5 mL) that contained 0 (control), 0.25, 0.50, 0.75, 1.00, 1.25, or 1.50 mg of SDA supplemented to 33 mg (DM basis) of commercial total mixed ration based on corn silage, for dairy cows, were incubated for 72 h at 39°C. The content of most fatty acids in whole freeze-dried cultures was affected by SDA supplementation. Branched-chain fatty acids decreased linearly (P < 0.01), and odd-chain fatty acids decreased quadratically (P < 0.01), particularly from 1.00 mg of SDA and above, whereas most C18 fatty acids increased linearly or quadratically (P ≤ 0.04). Stearidonic acid concentrations at 72 h of incubation were very small (<0.6% of total fatty acids and ≤0.9% of added SDA) in all treatments. The apparent biohydrogenation of SDA was extensive, but it was not affected by SDA concentration (P > 0.05). Biohydrogenation followed a pattern similar to that of other C18 unsaturated fatty acids up to 1.00 mg of SDA. Stearic acid (18:0) and vaccenic acid (18:1 trans-11) were the major fatty acids formed, with the latter increasing 9-fold in the 1.00 mg of SDA treatment. At greater inclusion rates, 18:0 and 18:1 trans isomers decreased (P ≤ 0.03), accompanied by increases in unidentified 18:3 and 18:4 isomers (P = 0.02), suggesting that the biohydrogenation pathway was inhibited. The present results clearly indicate that SDA was metabolized extensively, with numerous 18:4 and 18:3 products formed en route to further conversion to 18:2, 18:1 isomers, and 18:0.     

Use of Tannic Acid as Dough Oxidizing and Vitamin C Protective Agent

Trials with tannic acid in three concentrations (0.1, 0.2, and 0.3%) in a wheat flour dough were run to test its property to preserve the ascorbic acid degradation during baking and its performance in the dough viscoelasticity measured by its extensigraphic properties. The addition of tannic acid to the dough in the cited concentrations increased its resistance to extension (RE) and consequently reduced its extensibility (E) in the same way that ascorbic acid performed but using concentrations 10× smaller. In a dough containing ascorbic acid 0.02% and tannic acid 0.3%, the ascorbic acid retention after 10 days of storage was 34.8%, which represents 154% of the recommended daily intake of vitamin C by FAO/WHO (2002) for an adult (19–65 years old). The addition of tannic acid to the dough also increased the bread specific volume.