ABSTRACT Entomofauna associated with decaying cadavers may be useful in criminal investigation, either through the development of immature insects of interest or through entomological succession in corpses. These factors may vary if the insects are exposed to toxic substances that can modify the insect's developmental cycle, as well as its own occurrence, which would imply significant changes in the results of any investigation. However, there are few studies on how contamination by toxic compounds can affect the action of insects on carcasses and their consequence for forensic expertise. Therefore, this study aimed to test the hypothesis that the normal visitation of flies and beetles is altered in insecticide-contaminated carcasses. The experiment was carried out in a sugarcane plantation, using pig carcasses contaminated with insecticide and the same number of carcasses without any type of contamination as a control. In all experiments, the contaminated carcasses reached the final phase of decomposition in a longer time than the uncontaminated carcasses of the control group. A total of 2.767 specimens were collected and identified, 2.103 individuals from the order Diptera and 664 from the order Coleoptera. There was a significant geometric regression adjustment during the decomposition phases only for the control group, different from the contaminated carcasses in which this pattern did not occur. Results show that contamination by insecticide alters decomposition time and phase, altering the action of flies and beetles, affecting the abundance, composition of species as well as their activities, which can alter the data used by experts in criminal experts.

Grapes are among the most widely cultivated fruits in the world, with the majority of Brazilian production focusing on natural grape juice. In this work, a total of 40 samples of 2 types of natural grape juice were analyzed for the presence of 86 pesticide residues, with multiresidue extraction based on modified QuEChERS, by liquid chromatography with high-resolution mass spectrometry (LC-HRMS). Limits of detection and quantification were below 6 µg L-1 and 20 µg L-1, RSD < 20%, R2 > 0.99 and recovery ranged from 80 and 120%. Thus, the developed method was validated and good performance characteristics such as linearity, trueness, repeatability and inter-day precision were obtained. As results, 7 pesticides were detected in real samples (azoxystrobin, benalaxyl, carbendazim, tebuconazol, thiophanate-methyl, pyriproxiphen and pyrimethanil). The method was successfully validated for simultaneous evaluation of 86 multiclass pesticides residues levels, which was applied in 40 natural white and red grape juice market samples. The limits of quantification (LOQs) were low enough and the method was tested on samples showing its applicability, and therefore, this method can be used in routine analysis. Also, this work therefore also serves as an alert regarding the contamination of processed products.

Connaraceae is a plant family usually used in traditional medicine. Recently, we have reported the chemical composition and biological activity of 39 species around the world. This work highlights the application of these species to diabetes control, which has been reported at least to half of this family. In this line, there are several species of the Connaraceae without scientific evidence of traditional use, among these the four species study here. Thus, this work aims the chemical composition prospection of Connarus blanchetii, Connarus regnellii, Connarus suberosus and Rourea glazioui, as well as the identification of possible bioactivity. The leaves of these four species were collected, prepared and submitted to different extractive methods (aqueous decoction and infusion and ethanolic maceration), these being tested in a preliminary phytochemical investigation and subjected to antioxidant assay with 2,2-diphenyl-1-picrylhydrazyl and ferric reducing antioxidant power. Then, we selected the maceration extract to continue for fractions, with the ethyl acetate and n-butanol presenting the best results with antioxidant and anti-advanced glycation end products (AGEs) activity potential. Finally, the chemical composition was determinate by high-resolution mass spectrometry (HRMS) in combination with Global Natural Products Service (GNPS) data bank. As a result, this study indicated the presence of 29 phenolics compounds with reported activity as antioxidant and with potential of protein glycation, supported the diabetes activity of this plants. The n-butanolic fraction of R. glazioui showed compounds such as apigenin, kaempferol, quercetin, myricetin and chlorogenic acid, which have generated a half maximal inhibitory concentration (IC50) of 36.5 µg mL 1 for oxidative glycation inhibition, being highlighted as the most active.

ABSTRACT Corpses in Brazil are commonly hidden in sugarcane plantations in the attempt to delay their finding and hinder the solution of the crime. On the other hand, these plantations are regularly sprayed with insecticides for pest control. Until now no study has reported the effects of insecticides on ant fauna. This study aimed to test the hypothesis that if a body hidden in a monoculture is accidentally contaminated by an insecticide, both the carcass decomposition pattern and the Formicidae fauna will be affected. To accomplish this, pig carcasses contaminated and non-contaminated were placed in a sugarcane monoculture environment and subsequently examined for data collection every 24 hours. The concentration used to contaminate the carcasses was 20 grams per liter of thiamethoxam. The decomposition patterns of contaminated carcasses were changed, in turn affecting the behavior of Formicidae fauna. A total of 5318 ants were collected, 3397 in contaminated carcasses and 1919 in non-contaminated carcasses, and 30 species of 11 genera were identified. According to the analysis, there are no differences between the composition of species between contaminated and non-contaminated carcasses, however, a significant difference was observed in the composition of species along the stages of decomposition between the two types of carcasses. Therefore, our hypothesis has been confirmed, contaminated carcasses undergo changes in their normal pattern of decomposition and the fauna of ants that act on them. As this group of insects has great importance for forensic sciences, the analysis of the experts should take these results into account.

The synthesis of 3-alkyl-5-trifluoromethyl-1H- pyrazole-1-carboxamides, 3-alkyl-5-trifluoromethyl-1H-pyrazole-1-thiocarboxamides, and 2-(3-alkyl-5-trifluoromethyl-1H-pyrazol-1-yl)-thiazoles derivatives are reported. [3 + 2] cyclocondensations for a series of long alkyl chain 1,1,1-trifluoro-4-methoxyalk-3-en-2-ones and semicarbazide or thiosemicarbazide were carried out in ethanol, an eco-friendly medium. The series of trifluoromethyl-1H-pyrazol-1-yl-thiocarboxamide following a [3 + 2] cyclocondensation with 2-bromoacetophenone were converted into two series of 2-(3-alkyl-5-trifluoromethyl-1H-pyrazol-1-yl)-thiazoles. Good yields (69-96%) of the isolated products were obtained. The structures of the new long alkyl chain 1H-pyrazoles and 2-(1H-pyrazol-1-yl)thiazoles were characterized using 1H, 13C, and 19F nuclear magnetic resonance (NMR) spectroscopy and electrospray ionization tandem mass spectrometric (ESI MS/MS) data. Moreover, some of the products were evaluated for their antimicrobial activity against Gram-negative Escherichia coli American Type Culture Collection (ATCC) 35218, Salmonella enteritidis ATCC 13076, and Pseudomonas aeruginosa ATCC 15692; and Gram-positive Staphylococcus aureus ATCC 6538, methicillin resistant Staphylococcus aureus (MRSA clinical isolate), Streptococcus sp. (clinical isolate), and Candida albicans ATCC 14053 and Candida krusei ATCC 6258 fungi. All the tested 1H-pyrazoles exhibited antibacterial and antifungal activities at the tested concentrations. The compounds from series 4 were found to be powerful against MRSA.

Abstract Breast cancer is one of the leading types of cancer worldwide, and the search for new treatment options are crucial. Nonsteroidal anti-inflammatory drugs (NSAIDs) -specially ibuprofen and diclofenac-, have shown antitumoral effect against several types of cancer. The synthesis of organometallic compounds has shown significant improvements in pharmacological properties and efficacy of organic molecules. Two zinc II ternary complexes containing the NSAIDs diclofenac and ibuprofen and nicotinamide neutral linker (Nic) were obtained by the two-step solvent metalligand complexation method. The compounds Zn2(Diclof)4(Nic)2 (complex 1) and Zn2(Ibup)4(Nic)2 (complex 2) were tested in breast cancer cell lines (4T1, MCF-7 and MDA-MB-231) to evaluate their cytotoxicity, comparing to ibuprofen and diclofenac as controls. We found that both complex 1 and 2 exerted more than 60% reduction in 4T1 viability at 250µM, and complex 2 decreased cell viability at 250 µM and 137.5 µM in MCF-7 (34.35% and 26.42% reduction, respectively) and in MDA-MB-231 (57.2% and 22.88% reduction, respectively), all compared to controls. Complex 1 was selective only in MCF-7, and complex 2 was selective in both MCF-7 and MDA-MB-231. In summary, our data showed that the cytotoxic effect of complex 1 and 2 is increased comparing to their original NSAID in different breast cancer cell lines, highlighting their potential anti-tumoral activity.

This work aims the synthesis of amidino pyrazolines by the cyclocondensation reaction between 3-(hetero)aryl-1-(2-hydroxyphenyl)enones and aminoguanidine hydrochloride under sonochemical conditions. Thirteen new compounds were synthesized in 15-83% of yield after sonication for 30 min without purification by chromatography. Furthermore, antimicrobial activities of the synthesized compounds were investigated by in vitro minimum inhibitory concentration (MIC) in a panel of four bacterial strains and four Candida yeasts. As result, the 5-(4-bromophenyl)-3-(2-hydroxyphenyl)-4,5-dihydro-1H-pyrazole-1-carboximidamide hydrochloride was identified as the most active against gram-positive S. aureus and E. faecalis with MIC of 7.8 µg mL−1, similar to the value showed by chloramphenicol, which was used as standard.

This paper reports the DNA interaction and cytotoxicity of binary and ternary copper(II) complexes of valproic acid with phenanthroline or bipyridine and the complementary characterization of Cu(Valp)2Bipy by crystallography. Circular dichroism, plasmid and oligonucleotide assays have shown that the complexes interact with DNA in different manners and are able to cleave plasmid DNA and oligonucleotides at concentrations from 10 to 1000 mol L-1. The plasmid DNA cleavage is enhanced 650, 375 and 285 times by photo activation with UVB light for the complexes Cu(Valp)2Phen, Cu(Valp)2Bipy and Cu2(Valp)4, respectively. Cytotoxicity assays demonstrated that V79 cells were more sensitive to CuII derivatives than sodium valproate as evaluated by 3-(4,5-dimethylthiazol-2yl)-2,5-diphenyl tetrazolium bromide (MTT) and clonogenic assays, where the cytotoxic profile of the compounds was: Cu(Valp)2Phen higher than Cu(Valp)2Bipy, higher than Cu2(Valp)4. Therefore, we report two copper complexes, which interact with DNA and promote its cleavage, leading to an enhanced cytotoxicity when compared to valproic acid.

The synthesis of 5-[2-(trifluoromethylheteroaryl)-ethyl]-1,3,4-oxadiazoles derived from levulinic acid is reported. Cyclocondensations [4 + 1] between four different 5-[2-(trifluoromethylheteroaryl)propionylhydrazides derived from methyl 7,7,7-trifluoro-4-methoxy-6-oxo-4-heptenoate obtained from levulinic acid, and electrophilic orthoesters RC(OR1)3 (where R = H, Me, Ph) and CS2 were carried out in a mild medium. Good yields (69-96%) of isolated products were obtained. The structures of the new ethylene-spaced biheterocycles were characterized using 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and electrospray ionization coupled to tandem mass spectrometric (ESI MS/MS) data.

ABSTRACT Piper aduncum found naturally in the Amazon and southeastern Brazil, is known for its secondary metabolites that have activity on insects. Anticarsia gemmatalis and Spodoptera frugiperda are among the major insect pests associated with agricultural production. This research evaluated the biological activity of hexane, ethyl acetate, and ethanol extracts of P. aduncum leaves on mortality and duration of larval and pupal periods, as well as weight, width, and length of A. gemmatalis and S. frugiperda pupae. The mortality of A. gemmatalis larvae in trials with P. aduncum extracts were 93.3% (hexane) and 90% (ethyl acetate), estimating LC50 of 6.35 and 5.79 mg/mL, respectively. Mortality in S. frugiperda submitted to the hexane extract ranged from 3.33% to 96.66% (LC50 of 8.22 mg/mL). The ethanol extract induced low mortality (3.33% to 23.33%). The P. aduncum extracts did not affect the development of S. frugiperda pupae. In A. gemmatalis differences in weight and length occurred. The chemical characterization was by GC-MS, which revealed that the major constituent in the hexane extract of P. aduncum was apiol (90.7%). P. aduncum extracts are important and promising components to manage A. gemmatalis and S. frugiperda, which cause extensive production losses.

In present times, the Brazil is in the middle of the largest pesticide consumers worldwide, which demands proper control of environmental contamination. This study evaluated herbicides, acaricide, insecticides and fungicides in water and sediment carried-out from Lageado Tacongava hydrographic basin, Rio Grande do Sul, Brazil. For analysis, a QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe), and/or SPE (Solid-Phase Extraction) using HPLC (High Performance Liquid Chromatography) with MS (Mass Detector) was optimized. As result, the Linearity R2 > 0.99; Recuperation between 78 a 117%; and RSD < 20% for the 70 compounds simultaneously analyzed. The Acetamiprid, Azoxystrobin, Bendiocarb, Fenamidone, metribuzin, Pendimethalin, pyridaben, Thiophanate-methyl and Truflumizole found in water, and Acetamiprid, Azoxystrobin, Bendiocarb, boscalid and thiophanate-methyl in sediment, at concentrations from 0.1 µg kg-1 to 39.6 µg kg-1. Standard of pesticide residues in water and sediment studies are needed to evaluate such contamination. Regional samplings standard, as was done here, will be useful in a future water resources contamination mapping.

Vários compostos naturais voláteis produzidos pelo metabolismo secundário de plantas têm demonstrado ação antimicrobiana comprovada, permitindo a sua utilização no controle de fitopatógenos. Apresentam também, baixo impacto ambiental em comparação aos pesticidas convencionais. Os óleos essenciais apresentam esses compostos que podem ser encontrados em várias espécies de plantas, tais como Lippia alba (Mill.) N.E. Brown (Verbenaceae). Óleos essenciais de quatro quimiotipos de L. alba, caracterizados por seus compostos majoritários, cânfora, citral, linalol e cânfora/1,8-cineol, foram testados contra o fitopatógeno Alternaria solani Sorauer (Pleosporaceae), que causa pinta preta em tomates e é responsável por grandes perdas econômicas na produção. A ação antifúngica dos óleos essenciais foi testada in vitro utilizando meio de cultura batata dextrose ágar (BDA) nas concentrações 0,1, 0,5, 1,0, 1,5 e 2,0 µL mL-1 dos óleos essenciais. O quimiotipo que apresentou o melhor desempenho foi citral, mostrando inibição significativa em comparação aos outros a partir da concentração 0,5 µL mL-1. O óleo essencial do quimiotipo linalol foi eficiente a partir da concentração 1,5 µL mL-1. Porém, o quimiotipo cânfora não apresentou ação contra o fitopatógeno. Além disso, os óleos essenciais não tiveram nenhum efeito notável sobre a germinação e crescimento de tomate. Em conclusão, estes óleos essenciais apresentaram ação fungicida contra A. solani.

Several volatile natural compounds produced by plant secondary metabolism have been proven to present antimicrobial action, enabling their use in phytopathogen control. They also present low environmental impact when compared to conventional pesticides. Essential oils contain these compounds and can be found in several plant species, such as Lippia alba (Mill.) N.E. Brown (Verbenaceae). Essential oils of four chemotypes of L. alba, characterized by their major compounds, namely camphor, citral, linalool and camphor/1,8-cineole, were tested against the phytopathogen Alternaria solani Sorauer (Pleosporaceae), which causes early blight on tomatoes and is responsible for great economic losses regarding production. Essential oils antifungal action was tested in vitro using potato dextrose agar medium with essential oil concentrations at 0.1, 0.5, 1.0, 1.5 and 2.0 µL mL-1. The chemotype that had the best performance was citral, showing significant inhibition compared to the others, starting at the 0.5 µL mL-1 concentration. The essential oil belonging to the linalool chemotype was efficient starting at the 1.5 µL mL-1 concentration. Conversely, the camphor chemotype did not show any action against the phytopathogen. Moreover, the essential oils had no remarkable effect on tomato germination and growth. In conclusion, these essential oils presented fungicidal action against A. solani.

RESUMO Salvia officinalis (Lamiaceae) é muito utilizado no sul do Brasil como condimento, tempeiro e chá para o tratamento de várias doenças. O objetivo deste estudo foi caracterizar compostos químicos no extrato hidroalcoólica (ExtHS) e aquosas (ExtAS) de Salvia officinalis (L.) por cromatografia gasosa acoplado a espectrometria de massa (GC-MS) e pela espectrometria de ionização por electrospray de alta resolução acoplado a massas (ESI-QTOF MS/MS), avaliar a capacidade in vitro para eliminar o radical livre 2,2-difenil-1-picrilhidrazil (DPPH•) e 2,2'-azino-bis (6-3-etilbenzotiazolina-sulfónico) (ABTS•+), atividade da catalase (CAT-like) e superóxido dismutase (SOD-like), além disso, atividade citotóxica por ensaio MTT, alterações na morfologia celular por Giemsa e mecanismo de apoptose induzida por anexina V/iodeto de propídio. A identificação química revelou a presença de ácidos e compostos fenólicos nos extratos de sálvia. Na análise antioxidante in vitro ambos os extratos indicaram atividades promissoras. O ensaio citotóxico em células tumorais (HEp-2, HeLa, A-549, HT-29 e A-375) e em não-tumoral (células HEK-293 e MRC-5), mostraram seletividade para celulas tumorais. A imunicitoquímica apresentou a maioria das células tumorais nos estágios tardios de processo de apoptose e necrose. Tendo em conta os resultados aqui apresentados, Salvia officinalis brasileira (L.) usada como condimento e chá pode proteger o corpo de algumas doenças, em particular aquelas que envolvem estresse oxidativo, como desordens neurodegenerativas, inflamação e câncer.

ABSTRACT Salvia officinalis (Lamiaceae) has been used in south of Brazil as a diary homemade, in food condiment and tea-beverage used for the treatment of several disorders. The objective of this study was to characterize chemical compounds in the hydroalcoholic (ExtHS) and aqueous (ExtAS) extract from Salvia officinalis (L.) by gas chromatography-mass spectrometry (GC-MS) and by high-resolution electrospray ionization mass spectrometry (ESI-QTOF MS/MS), evaluate in vitro ability to scavenge the free radical 2,2-diphenyl-1-picrylhydrazyl (DPPH•) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS•+), catalase (CAT-like) and superoxide dismutase (SOD-like) activity, moreover cytotoxic by MTT assay, alterations on cell morphology by giemsa and apoptotic-induced mechanism for annexin V/propidium iodide. Chemical identification sage extracts revealed the presence of acids and phenolic compounds. In vitro antioxidant analysis for both extracts indicated promising activities. The cytotoxic assays using tumor (Hep-2, HeLa, A-549, HT-29 and A-375) and in non-tumor (HEK-293 and MRC-5), showed selectivity for tumor cell lines. Immunocytochemistry presenting a majority of tumor cells at late stages of the apoptotic process and necrosis. Given the results presented here, Brazilian Salvia officinalis (L.) used as condiment and tea, may protect the body against some disease, in particularly those where oxidative stress is involved, like neurodegenerative disorders, inflammation and cancer.

Este caso para ensino descreve a trajetória da internacionalização da marca Aliança, uma marca de suco de uva integral e orgânico da Cooperativa Nova Aliança, localizada em Caxias do Sul (RS). O caso se desenvolve a partir do interesse da técnica da cooperativa Márcia e do cooperado Márcio em marcar uma reunião com o presidente da cooperativa para discutir a ampliação para novos mercados. É importante para a cooperativa a sua inserção no mercado internacional. O caso apresenta o processo da primeira exportação e traz uma discussão sobre decisões importantes que ocorreram na negociação internacional, para a inserção da marca no mercado líbio entre o importador Mr. Harmed, a coordenadora da cooperativa, Sra. Ana e o consultor da empresa júnior Lorran. O caso atende os seguintes objetivos de ensino: compreender como se dá o processo de internacionalização da marca na linha de sucos de uva da cooperativa, verificar os principais desafios encontrados para a consolidação do preço de exportação, identificar as principais exigências documentais e verificar a(s) estratégia(s) de internacionalização para a ampliação da marca no mercado internacional. O caso pode ser aplicado nas disciplinas de negociações internacionais, marketing internacional, estratégia de inserção internacional, logística, câmbio e sistemática de comércio exterior.

This teaching case describes the path to the internationalization of the brand Aliança, a brand for organic whole grape juice, from the Cooperative Nova Aliança, located in Caxias do Sul (RS). The case is developed from the interest of the cooperative technician Marcia and the cooperated Marcio to have an appointment with the president of the cooperative to discuss expanding into new markets. It is important for the cooperative its insertion in the international market. The case presents the process of the first export and brings a discussion about the important decisions that have occurred in the international negotiations, in order to introduce the brand in the Lybian market, between the importer Mr. Harmed, the coordinator of the company, Ms. Anna and the junior company consultant Lorran. The case meets the following learning objectives: to understand the process of internationalization of the brand in the line of juices of a cooperative, to check the main challenges encountered in consolidating the export price, to identify the key documentary requirements and to verify the strategy(ies) for the internationalization expansion of the brand in the international market. The case can be applied in the disciplines of international negotiations, international marketing, international insertion strategy, logistics, and foreign trade systematic and exchange.

Este caso para la enseñanza describe la trayectoria de la internacionalización de la marca Aliança, una marca de jugo de uva entero y orgánico de la Cooperativa Nova Aliança, situado en Caxias do Sul (RS). El caso se desarrolla a partir del interés de Márcia, la técnica de la cooperativa y del cooperado Márcio en concertar una reunión con el Presidente de la cooperativa para discutir la expansión a nuevos mercados. Es importante para la cooperativa su inserción en el mercado internacional. El caso presenta el proceso de la primera exportación y trae un debate sobre las decisiones importantes que ocurrieron en la negociación internacional para la inserción de la etiqueta en el mercado libio entre el importador, Sr. Harmed, la coordinadora de la cooperativa, Doña Ana y el consultor de la empresa junior, Lorran. El caso cumple con los siguientes objetivos educativos: comprender cómo se realiza el proceso de internacionalización de la marca en la línea de jugos de uva de la cooperativa, verificar los principales retos para la consolidación del precio de exportación, identificar los principales requisitos documentales y revisar las estrategias de internacionalización para la expansión de la marca en el mercado internacional. El caso puede ser aplicado en las disciplinas de negociaciones internacionales, marketing internacional, estrategia de inserción internacional, logística, cambio y sistemática de comercio exterior.

A biflorina é uma o-naftoquinona com comprovados efeitos citotóxicos frente a células tumorais além de atividades antimicrobiana, antitumoral e antimutagênica. A biflorina é um composto isolado das raízes da planta Capraria biflora L.(Schrophulariaceae), originária das Antilhas e da América do Sul, que está localizada em zonas temperadas e tropicais. Este composto mostrou uma potente atividade contra microorganismos gram-positivos e bactérias álcool-ácido resistentes. Tem mostrado eficiência em inibir a proliferação celular em linhagens tumorais CEM, HL-60, B16, HCT-8, MCF-7. Recentemente, a linhagem tumoral SK-Br3 foi tratada com biflorina e demonstrou importante efeito citotóxico. Neste artigo, relatamos informações relacionadas com os primeiros estudos de caracterização estrutural, bem como os últimos relatos sobre a atividade biológica desta molécula.

Biflorin is an o-naphthoquinone with proven cytotoxic effects on tumor cells showing antimicrobial, antitumor and antimutagenic activities. Biflorin is an isolated compound taken from the roots of the plantCapraria biflora L. (Schrophulariaceae), indigenous of the West Indies and South America, which is located in temperate or tropical areas. This compound has shown to be strongly active against grampositive and alcohol-acid-resistant bacteria. It has been efficient in inhibiting the proliferation tumor cell lines CEM, HL-60, B16, HCT-8 and MCF-7. Recently, SK-Br3 cell line was treated with biflorin showing important cytotoxic effects. In this article, information related to the first structural characterization studies are presented, as well as the latest reports concerning the biological activity of this molecule.