Synthesis and insecticidal activity of new pyrethroids

BACKGROUND: Pyrethroids are among the most potent pesticides known, with great potential for structural variation with retention or enhancement of potency. The simple methyl ester is easier to prepare (at least one step shorter) than the more complex pyrethroids modified on the alcohol moiety. The objective was to synthesise methyl esters of pyrethroid acids containing an aromatic ring on the acid moiety and evaluate their biological activity against Ascia monuste orseis Latr., Tuta absoluta Meyrick, Periplaneta americana (L.), Musca domestica L. and Sitophilus zeamais (Motsch.). RESULTS: The synthetic sequence required seven steps: protection of the hydroxyl groups of D ‐mannitol, diol oxidative cleavage with sodium metaperiodate, alkene formation by Wittig reaction with methoxycarbonylmethylidene(triphenyl)phosphorane, cyclopropanation, acetal hydrolysis with perchloric acid and oxidative cleavage with sodium metaperiodate gave methyl (1S, 3S)‐3‐formyl‐2,2‐dimethylcyclopropane‐1‐carboxylate. The final step comprised reaction of the aldehyde with five different aromatic phosphorus ylides to give the pyrethroids. CONCLUSION: An efficient and versatile synthesis of ten new pyrethroid methyl esters has been accomplished from the readily available D ‐mannitol in seven steps. All compounds showed insecticidal activity, and methyl (1S, 3S)‐3‐[(Z)‐2‐(4‐chlorophenyl)vinyl]‐2,2‐dimethylcyclopropane‐1‐carboxylate was the most active, killing 90% of A. monuste orseis and 100% of T. absoluta and P. americana. Copyright © 2009 Society of Chemical Industry     

Performance of dual and triple fungicide premixes for managing soybean rust across years and regions in Brazil: A meta-analysis

Soybean rust in Brazil is currently controlled with several commercial fungicide premixes composed of demethylation inhibitors (EPOXiconazole, CYPRoconazole, PROThioconazole, TEBUconazole), quinone-outside inhibitors (AZOXystrobin, TriFLoXystrobin, PYRAclostrobin, PICOxystrobin), and succinate demethylation inhibitors (BENZovindiflupyr, BIXaFen, FLUXapyroxad). Here, we summarize the performance of eight premixes evaluated in 177 cooperative trials conducted in 46 locations across 10 states from 2015 to 2020. All fungicide treatments were sprayed three times starting at R1/R2. Percentage control (, %), from back-transforming meta-analytic estimates of the log of the ratio, ranged from 56.2% (PICO + CYPR) to 76.8% (BIXF + TFLX + PROT). Estimates of mean yield difference (, kg/ha) between fungicide-treated and untreated plots were greatest for BIXF + TFLX + PROT (1,080) followed by PICO + BENZ (1,010), PYRA + EPOX + FLUX (981.5), AZOX + BENZ (910), TFLX + PROT (891), PICO +TEBU (682), TFLX + CYPR (646), and PICO + CYPR (600). Significant declines in both and in as little as 4 years were detected for AZOX + BENZ (35.3%; 550 kg/ha) and PICO + BENZ (15.5%; 359.8 kg/ha). Variance in was reduced by the inclusion of baseline severity as covariate. In trials where baseline disease was ≥70%, yield was 250 kg/ha greater compared to areas with low baseline disease. Disease control and yield response were generally greater in the south-east, where the frequency of profitable scenarios was 30% higher on average than in the north-west. Results of this meta-analysis are critical for supporting decisions during planning of fungicide programmes.     

Effect of Marcela Extract (Achyroclines satureiodes) on the Shelf Life of Minced Tilapia (Oreochromis niloticus) Sausages

The effect of marcela extract (ME) on the shelf life of minced tilapia sausages was evaluated in this study. The level of phenolic compounds in the ME was 114.1 ± 2.9 mg GAE/g extract, and the DPPH free radical scavenging activity was 94.95 ± 1.34%. The ME protected the samples from color changes during storage. The addition of 0.5 and 0.75% ME significantly decreased lipid oxidation and microbial growth. The ME did not impact the sausages’ sensory quality, and the addition of 0.75% prevented sensory rejection during storage.     

Serum and Tissue Steroid Hormone Levels in Canine Mammary Tumours: Clinical and Prognostic Implications

Hormonal dependency of canine mammary tumours (CMT) has been studied over the last few decades. However, studies assessing the prognostic and predictive potential of serum and/or tissue steroid hormone levels are still scarce in CMT. To the best of our knowledge, this is the first report relating serum and tissue levels of steroid hormones and prognosis in dogs. Serum and tumour tissue from 45 female dogs with spontaneous CMT were included in the study. Moreover, serum and normal mammary tissue from 13 healthy female dogs were also included as controls. Steroid hormones were determined by competitive enzyme immunoassay. Overall, levels of steroid hormones in serum and tissue homogenates were significantly different between malignant and benign mammary tumours (p < 0.01), except for progesterone (P4) serum levels that revealed no statistical differences between groups. In malignant tumours, oestrone sulphate (SO4E1), dehydroepiandrosterone (DHEA), androstenedione (A4), testosterone (T) and P4 elevated tissue concentrations were significantly associated with tumour relapse and/or distant metastasis during follow‐up. A significant association was found between elevated tissue SO4E1 (p = 0.003), 17β‐oestradiol (E2) (p = 0.036), DHEA (p = 0.022), A4 (p = 0.001) and P4 (p = 0.013) concentrations and shorter disease‐free survival and overall survival in female dogs with malignant mammary tumours. The high levels of tissue steroids found in cases of poor prognosis open the possibility of additional new therapeutic approaches. Future clinical trials will be needed to clarify the usefulness of targeting steroid hormones in the treatment of this neoplastic disease.     

Experimental reproduction of winter dysentery in lactating cows using BCV -- comparison with BCV infection in milk-fed calves

Infection models were developed for adult cows and for young calves using the same strain of bovine coronavirus (BCV), which for the first time allows experimental reproduction of winter dysentery (WD) in seronegative lactating cows. The cattle were infected through direct contact with an experimentally inoculated calf. All experimental cattle shed faecal BCV with development of diarrhoea, being profusely watery with small amounts of blood in the most severely affected animals, including both cows and calves. The cows, in contrast to the calves, showed depressed general condition and appetite leading to a marked decrease in milk yield. Further age-associated differences were a shorter incubation period in the two youngest calves, but with milder fever and milder decrease in white blood cell counts. These findings shed light on the apparent epidemiological differences between WD and calf BCV diarrhoea suggesting that, (1) the same strains of BCV cause natural outbreaks of calf diarrhoea and WD, (2) seronegative cows are more severely affected by the infection than seronegative conventionally reared calves, and (3) unaffected general condition in diarrhoeic calves may lead to underestimation of the occurrence of calf diarrhoea in WD outbreaks.In response to infection, all cattle produced early interferon type 1 in serum and, except for one calf, in nasal secretions. A finding not previously reported is the detection of interferon type 1 responses in bovine milk. All cattle developed high IgM antibody responses and long-lasting IgA antibody responses both systemically and locally. The serum IgM antibody responses came earlier in most of the calves than in the cows. Prolonged IgM antibody responses were detected in serum and milk, while those in nasal secretions were much shorter. BCV-specific IgA was present in nasal secretions from all cattle throughout the 6 months follow-up. The IgA antibody response in serum was detected up to 17 months post-infection and the duration showed an age-related variation indicating a more prominent IgA memory in the adult cattle and in the older calves than in the younger ones. BCV-specific IgG was detected in all cattle during the experimental period of up to 22 months. In conclusion, WD was reproduced in seronegative lactating cows. The cows showed a more severe general diseases than seronegative calves infected concurrently. Very long-lasting IgA antibody responses were detected both systemically and locally.     

The Effects of the Decaffeination of Coffee Samples on Platelet Aggregation in Hyperlipidemic Rats

The effect of coffee on cardiovascular diseases is still controversial. It is known that the process of decaffeination may influence the chemical constitution and, therefore, the biological effects of coffee. This study thus evaluated the effects of decaffeination on the levels of total phenols and chlorogenic acids in Coffea arabica L. samples, as well as the effects of ingesting both integral and decaffeinated coffee on the lipid profile and hemostatic and hematological parameters in normal and hyperlipidemic rats. Samples of integral and decaffeinated lyophilized coffee (Coffea arabica L., planted in Brazil) were used for chemical analysis (total phenols, chlorogenic acid and caffeine contents). For the bioassays, coffee beverages were prepared with non-lyophilized samples (10 % w/v) and were filtered and administered to animals by gavage (7.2 mL/kg/day) over 30 days. On the 31st day after beginning the treatment with coffee beverages, hyperlipidemia was induced to the animals by administering Triton WR-1339 (300 mg/kg body weight). On day 32, blood was taken to determine the lipid profile, platelet aggregation, prothrombin time, partially activated thromboplastin time and hemogram. The contents of both phenolic compounds and chlorogenic acid in the integral coffee beverage were significantly lower than those in the decaffeinated coffee beverage. The animals treated with Triton WR-1339 presented a mixed hyperlipidemia. Although the decaffeination process caused a relative increase in total phenols and chlorogenic acids, the coffee drinks were unable to change the lipid profile or the hemostatic and hematological parameters in the studied animals.     

Protein quality, antigenicity, and antioxidant activity of soy-based foodstuffs

Commercial soy-based foodstuffs, including beverages ( n = 15), cow's milk supplemented with soy isoflavones ( n = 1), snacks ( n = 1), and biscuits ( n = 2), were analyzed to find any link between alterations in protein quality, safety (antigenicity), functionality (antioxidant activity), and food processing. Protein content was analyzed by the Kjeldhal method and available lysine by OPA assay. Chromatographic (RP-HPLC) and electrophoretic (SDS-PAGE) protein profiles were obtained to monitor modifications in the structure of soy allergens. The antigenicity was estimated by immunoblotting against soy total antibodies. Total phenol content was measured by Folin-Ciocalteu, while peroxyl radical scavenging activity of the sample was determined by ORAC FL assay. Protein content did not differ of those declared by the producers. Lysine availability was higher in liquid soy beverages compared to that in other soy foodstuffs studied here. 7S and 11S soy allergens were detected by RP-HPLC and SDS-PAGE, respectively. Both data indicated changes in soy protein patterns due to processing of instant powdered soymilk, soy snacks, and biscuits. Immunoblotting assay showed modifications in the antigenic response of these foodstuffs based on soy, suggesting that their processing had altered the structure of soy allergens. RP-HPLC, SDS-PAGE, and immunoblotting resulted in adequate analytical approaches for detecting changes in protein structure due to processing and adulteration. Protein quality, antigenicity, and antioxidant activity of soy products can be affected as a function of the intensity of the thermal processing.     

Serum gastrin in canine chronic lymphocytic-plasmacytic enteritis

This study evaluates serum gastrin concentrations in dogs with chronic lymphocytic-plasmacytic enteritis, as well as its possible relationship with the severity of lesions present in the stomach. To achieve this aim, 5 dogs without gastrointestinal disease and 15 dogs with chronic lymphocytic-plasmacytic enteritis were included. Serum gastrin concentrations were significantly increased in dogs with chronic lymphocytic-plasmacytic enteritis compared with those in dogs without gastrointestinal disease. Also, there was a positive correlation between the severity of the gastric lesion and the serum gastrin concentration. Our findings indicate the possibility that gastrin plays a role in the etiology of an accompanying chronic antral gastritis in canine chronic lymphocytic-plasmacytic enteritis.