µQuEChERS Combined with UHPLC-PDA as a State-of-the-Art Analytical Approach for Quantification of Chlorpropham in Potato

Pesticides are chemicals used in agriculture to prevent insects, fungi, weeds, and other pests, from damaging crops. In addition, some types of pesticides are used after harvest as sprout suppressant agents help keeping the quality parameters of crops during storage. Nonetheless, its presence, even at trace levels, in food products is becoming a big challenge regarding human health. The current work aimed to develop and validate a sensitive and high-throughput analytical approach, based on a state-of-the-art microextraction technique—µQuEChERS, combined with ultra-high performance liquid chromatography equipped with a photodiode array detection system (UHPLC-PDA) to quantify isopropyl-N-(3-chlorophenyl) carbamate (chlorpropham), commonly used as efficient sprout suppressant stored potatoes, in raw and cooked potatoes cultivated in different geographical regions of Madeira Island (Portugal). Good results were obtained in terms of figures of the merit of the method, with correlation coefficients (R2 ) higher than 0.999 and recoveries between 94.5% to 125%. Method limit of detection (LOD) and limit of quantification (LOQ) were 0.14 µg/Kg and 0.43 µg/Kg, respectively, which are much lower than the accepted and legislated requirements by the European Union, which is 20 µg/Kg for chlorpropham. The concentration of chlorpropham in raw potatoes is significantly higher when compared to cooked samples, which revealed that the thermic treatment during cooking had a significant effect on its degradation. A significant decrease (90%, on average) was observed on chlorpropham levels.info:eu-repo/semantics/publishedVersio

Green extraction techniques as advanced sample preparation approaches in biological, food, and environmental matrices: A review

Green extraction techniques (GreETs) emerged in the last decade as greener and sustainable alternatives to classical sample preparation procedures aiming to improve the selectivity and sensitivity of analytical methods, simultaneously reducing the deleterious side effects of classical extraction techniques (CETs) for both the operator and the environment. The implementation of improved processes that overcome the main constraints of classical methods in terms of efficiency and ability to minimize or eliminate the use and generation of harmful substances will promote more efficient use of energy and resources in close association with the principles supporting the concept of green chemistry. The current review aims to update the state of the art of some cutting-edge GreETs developed and implemented in recent years focusing on the improvement of the main analytical features, practical aspects, and relevant applications in the biological, food, and environmental fields. Approaches to improve and accelerate the extraction efficiency and to lower solvent consumption, including sorbent-based techniques, such as solid-phase microextraction (SPME) and fabric-phase sorbent extraction (FPSE), and solvent-based techniques (μQuEChERS; micro quick, easy, cheap, effective, rugged, and safe), ultrasound-assisted extraction (UAE), and microwave-assisted extraction (MAE), in addition to supercritical fluid extraction (SFE) and pressurized solvent extraction (PSE), are highlighted.This research was funded by FCT (Fundação para a Ciência e a Tecnologia) through the CQM Base Fund, UIDB/00674/2020, Programmatic Fund, UIDP/00674/2020, and CEB—Centre of Biological Engineering, and by ARDITI (Agência Regional para o Desenvolvimento da Investigação Tecnologia e Inovação) through the project M1420-01-0145-FEDER-000005, Centro de Química da Madeira (CQM+; Madeira 14-20 Program). The authors also acknowledge FCT and the Madeira 14–20 Program to the Portuguese Mass Spectrometry Network (RNEM) through the PROEQUIPRAM program, M14-20 M1420-01-0145-FEDER-000008). ARDITI is also acknowledged for the postdoctoral fellowship granted to J.A.M.P. (Project M1420-09-5369-FSE-000001).info:eu-repo/semantics/publishedVersio

Integrative Effect of Carvedilol and Aerobic Exercise Training Therapies on Improving Cardiac Contractility and Remodeling in Heart Failure Mice

The use of b-blockers is mandatory for counteracting heart failure (HF)-induced chronic sympathetic hyperactivity, cardiac dysfunction and remodeling. Importantly, aerobic exercise training, an efficient nonpharmacological therapy to HF, also counteracts sympathetic hyperactivity in HF and improves exercise tolerance and cardiac contractility; the latter associated with changes in cardiac Ca2+ handling. This study was undertaken to test whether combined b-blocker and aerobic exercise training would integrate the beneficial effects of isolated therapies on cardiac structure, contractility and cardiomyocyte Ca2+ handling in a genetic model of sympathetic hyperactivity-induced HF (alpha(2A)/alpha 2C(-)adrenergic receptor knockout mice, KO). We used a cohort of 5-7 mo male wild-type (WT) and congenic mice (KO) with C57Bl6/J genetic background randomly assigned into 5 groups: control (WT), saline-treated KO (KOS), exercise trained KO (KOT), carvedilol-treated KO (KOC) and, combined carvedilol-treated and exercise-trained KO (KOCT). Isolated and combined therapies reduced mortality compared with KOS mice. Both KOT and KOCT groups had increased exercise tolerance, while groups receiving carvedilol had increased left ventricular fractional shortening and reduced cardiac collagen volume fraction compared with KOS group. Cellular data confirmed that cardiomyocytes from KOS mice displayed abnormal Ca2+ handling. KOT group had increased intracellular peak of Ca2+ transient and reduced diastolic Ca2+ decay compared with KOS group, while KOC had increased Ca2+ decay compared with KOS group. Notably, combined therapies re-established cardiomyocyte Ca2+ transient paralleled by increased SERCA2 expression and SERCA2: PLN ratio toward WT levels. Aerobic exercise trained increased the phosphorylation of PLN at Ser16 and Thr17 residues in both KOT and KOCT groups, but carvedilol treatment reduced lipid peroxidation in KOC and KOCT groups compared with KOS group. the present findings provide evidence that the combination of carvedilol and aerobic exercise training therapies lead to a better integrative outcome than carvedilol or exercise training used in isolation.Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG)Conselho Nacional de Pesquisa e DesenvolvimentoConselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Univ São Paulo, Sch Phys Educ & Sport, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Biosci, Santos, BrazilDept Circulat & Med Imaging, Trondheim, NorwayKG Jebsen Ctr Exercise Med, Trondheim, NorwayUniv Fed Minas Gerais, Dept Physiol & Biophys, Belo Horizonte, MG, BrazilUniv São Paulo, Heart Inst InCor, São Paulo, BrazilUniversidade Federal de São Paulo, Dept Biosci, Santos, BrazilFAPESP: FAPESP:2010/50048-1FAPESP: 06/56123-0CNPq: 302201/2011-4Web of Scienc

Ornato e despojamento no mundo fabril

O artigo investiga algumas das tendências da arquitetura gerada por fábricas - galpões industriais, moradias, igrejas, escolas, clubes etc. -, erguida no Brasil entre as duas últimas décadas do século XIX e as primeiras do XX. Apoia-se em amplo inventário, como base para um esforço de análise que se propõe a identificar os temas e usos predominantes dos ornatos aplicados a construções geradas por fábricas, as referências historicistas mobilizadas e eventuais rupturas de signos arquitetônicos tipológicos, e, no limite, a abolição de ornatos e dos referidos signos. Assim, de um lado, trata da penetração da linguagem eclética nessas construções, investigando o repertório formal utilizado em diferentes tipologias. De outro, trata da simultânea difusão de uma estética tipicamente fabril, fundamentada em noções de economia, eficiência, utilidade e funcionalidade. Mostra como tais noções se expressam ora em uma simplificação ou ausência de ornatos, ora no uso de ornatos cujos temas remetem ao mundo das máquinas; às vezes, no distanciamento ou abandono de signos arquitetônicos tipológicos consagrados; ou, ainda, no emprego de materiais produzidos industrialmente e que se difundiram a partir, sobretudo, da arquitetura de fábricas.The article examines some aspects of the architecture created for factories - warehouses, houses, churches, schools, clubs etc. -, built in Brazil between the two last decades of the nineteenth century and early of the twentieth century. The research relies on extensive inventory, the basis on which an analysis effort is realized that aims to identify the themes and predominant use of ornament applied to constructions produced by factories, the historicist references mobilized and eventual disruption of typological architectural signs, and, ultimately, the elimination of ornament and of those signs. Therefore, on one side, it deals with the penetration of the eclectic language in these buildings, by examining the formal repertoire used in different typologies. On the other side, it deals with simultaneous diffusion of a typical manufacturing aesthetic, based on notions of economy, efficiency, utility and functionality. It shows how such notions are expressed in either a simplification or the lack of ornament, sometimes in the use of ornament whose themes relate to the world of machines, sometimes in the detachment or abandonment of embodied architectural typological signs, or even the use of industrially produced materials that have spread from mainly the architecture of factories

Highly Active Microbial Phosphoantigen Induces Rapid yet Sustained MEK/Erk- and PI-3K/Akt-Mediated Signal Transduction in Anti-Tumor Human γδ T-Cells

BACKGROUND: The unique responsiveness of Vgamma9Vdelta2 T-cells, the major gammadelta subset of human peripheral blood, to non-peptidic prenyl pyrophosphate antigens constitutes the basis of current gammadelta T-cell-based cancer immunotherapy strategies. However, the molecular mechanisms responsible for phosphoantigen-mediated activation of human gammadelta T-cells remain unclear. In particular, previous reports have described a very slow kinetics of activation of T-cell receptor (TCR)-associated signal transduction pathways by isopentenyl pyrophosphate and bromohydrin pyrophosphate, seemingly incompatible with direct binding of these antigens to the Vgamma9Vdelta2 TCR. Here we have studied the most potent natural phosphoantigen yet identified, (E)-4-hydroxy-3-methyl-but-2-enyl pyrophosphate (HMB-PP), produced by Eubacteria and Protozoa, and examined its gammadelta T-cell activation and anti-tumor properties. METHODOLOGY/PRINCIPAL FINDINGS: We have performed a comparative study between HMB-PP and the anti-CD3epsilon monoclonal antibody OKT3, used as a reference inducer of bona fide TCR signaling, and followed multiple cellular and molecular gammadelta T-cell activation events. We show that HMB-PP activates MEK/Erk and PI-3K/Akt pathways as rapidly as OKT3, and induces an almost identical transcriptional profile in Vgamma9(+) T-cells. Moreover, MEK/Erk and PI-3K/Akt activities are indispensable for the cellular effects of HMB-PP, including gammadelta T-cell activation, proliferation and anti-tumor cytotoxicity, which are also abolished upon antibody blockade of the Vgamma9(+) TCR Surprisingly, HMB-PP treatment does not induce down-modulation of surface TCR levels, and thereby sustains gammadelta T-cell activation upon re-stimulation. This ultimately translates in potent human gammadelta T-cell anti-tumor function both in vitro and in vivo upon transplantation of human leukemia cells into lymphopenic mice, CONCLUSIONS/SIGNIFICANCE: The development of efficient cancer immunotherapy strategies critically depends on our capacity to maximize anti-tumor effector T-cell responses. By characterizing the intracellular mechanisms of HMB-PP-mediated activation of the highly cytotoxic Vgamma9(+) T-cell subset, our data strongly support the usage of this microbial antigen in novel cancer clinical trials