Abstract Melissopalynological techniques are used in the analysis of pollen grains. However, the adoption of methodologies considering cost-effectiveness, shorter preparation time and lesser toxic procedures for researchers is relevant. Thus, this study aimed to analyze different melissopalynological methodologies in polyfloral honey samples. Three melissopalynological protocols were applied to the samples using alcian blue dye, basic fuchsin, and the traditional acetolysis methodology without dye. After preparing the pollen samples, and analyzing them under an optical microscope, six botanical families were recorded, e.g., Amaranthaceae, Asteraceae, Bignoniaceae, Fabaceae, Malvaceae, and Myrtaceae. The methodologies investigated proved to be efficient for detecting pollen structures and identifying botanical families thereof. The alcian blue dye-based protocol allowed a greater separation and discrimination of pollen grains as compared to the basic fuchsin and acetolysis ones, where pollen conglomerates were often identified. Even though acetolysis has been the most used method in melissopalynological studies, it has been claimed to offer risks to users due to the manipulation of corrosive and toxic solvents (i.e., H2SO4), also being lesser cost-effective and more time-consuming. Thus, considering the cost-effectiveness, the alcian blue dye and basic fuchsin-based methods seem to be preferred, being as efficient as acetolysis for identifying pollen grains. However costeffectiveness, costeffectiveness cost effectiveness, effectiveness cost-effectiveness relevant Thus microscope recorded eg e g e.g. Amaranthaceae Asteraceae Bignoniaceae Fabaceae Malvaceae Myrtaceae thereof dyebased based ones identified studies i.e., ie i (i.e. H2SO4, H2SO4 HSO , H SO H2SO4) costeffective effective timeconsuming. timeconsuming consuming. consuming time-consuming fuchsinbased preferred e.g i.e. (i.e H2SO i.e

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. world 4 8 QuEChERS highresolution high resolution LCHRMS. LCHRMS LC HRMS . (LC-HRMS) L1 L 1 L- L1, 1, 20% R 099 0 99 0.9 120 120% Thus linearity trueness interday inter day obtained results azoxystrobin, azoxystrobin (azoxystrobin benalaxyl carbendazim tebuconazol thiophanatemethyl, thiophanatemethyl thiophanate methyl, methyl thiophanate-methyl pyrimethanil. pyrimethanil pyrimethanil) levels LOQs (LOQs applicability analysis Also products (LC-HRMS 09 9 0. 12

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. medicine Recently 3 world control line use here Thus blanchetii regnellii bioactivity collected aqueous maceration, , maceration) 2,2diphenyl1picrylhydrazyl 22diphenyl1picrylhydrazyl diphenylpicrylhydrazyl 2,2 diphenyl picrylhydrazyl 2 power Then fractions nbutanol n butanol antiadvanced anti advanced AGEs (AGEs Finally highresolution high resolution HRMS (HRMS GNPS (GNPS bank result plants nbutanolic butanolic R apigenin kaempferol quercetin acid IC50 IC (IC50 365 36 5 36. inhibition active 2diphenyl1picrylhydrazyl 22 2, IC5 (IC5 (IC

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.

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.

The genus Mikania ranks high in the list of best-selling natural products in the world. Its main distribution is in South America, but some species are found in Asia, North America and Africa. It is used for treating fever, rheumatism, colds and respiratory diseases, as well as snake bites and scorpion stings, due to its broad spectrum of action. There are approximately 430 species of this genus and only 12% have been studied, highlighting their chemical and pharmacological diversity. The main chemical groups are: coumarins and derivatives, sesquiterpenes, sesquiterpenes lactones, diterpenes, phytosterols/terpenoids and flavonoids. This review aims to supply useful references for scientists interested in natural products and the search for new compounds, from over the 300 already described for the genus.

Cinco derivados de 4-trifluorometil-2-(5-aril-3-stiril-1H-pirazol-1il)-pirimidinas e seis 5-aril-3-estiril-1-carboxamidino-1H-pirazois previamente sintetizados foram avaliados de acordo com suas propriedades antioxidantes e antimicrobianas. Estas atividades foram avaliadas por ensaios de DPPH e HRP/luminol/H2O2 quimioluminescência e suas atividades antimicrobianas (CIM). Os resultados foram bons para alguns compostos da série em certas concentrações em comparação direta com padrões.

Five previously synthesized 4-trifluoromethyl-2-(5-aryl-3-styryl-1H-pyrazol-1yl)-pyrimidines and six 5-aryl-3-styryl-1-carboxamidino-1H-pyrazole derivatives were screened for their antioxidant proprieties. The antioxidant activities were evaluated by using the DPPH and the HRP/luminol/H2O2 chemiluminescence assay systems and for their antimicrobial activity (MIC). The results were good for those series in some concentration in comparison with the standards.