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The essential oil of citronella (Cymbopogon winterianus) has several biological activities, among them the insect repellent action. Some studies showed that cinnamic acid esters can be applied as natural pesticides, insecticides and fungicides. In this context, the objective of the present work was to evaluate the production of esters from citronella essential oil with cinnamic acid via enzymatic esterification. Besides, the essential oil toxicity before and after esterification against Artemia salina and larvicidal action on Aedes aegypti was investigated. Esters were produced using cinnamic acid as the acylating agent and citronella essential oil (3:1) in heptane and 15 wt% NS 88011 enzyme as biocatalysts, at 70 °C and 150 rpm. Conversion rates of citronellyl and geranyl cinnamates were 58.7 and 69.0% for NS 88011, respectively. For the toxicity to Artemia salina LC50 results of 5.29 μg mL-1 were obtained for the essential oil and 4.36 μg mL-1 for the esterified oils obtained with NS 88011. In the insecticidal activity against Aedes aegypti larvae, was obtained LC50 of 111.84 μg mL-1 for the essential oil of citronella and 86.30 μg mL-1 for the esterified oils obtained with the enzyme NS 88011, indicating high toxicity of the esters. The results demonstrated that the evaluated samples present potential of application as bioinsecticide.

A laboratory experiment was developed to introduce undergraduate chemistry students to the chemical characterization of agroindustrial waste extracts by gas chromatography–mass spectrometry (GC–MS). The students prepared hexane and dichloromethane extracts from black pepper (Piper nigrum L.) waste. GC–MS analysis revealed the possible presence of sesquiterpenes and piperine, compounds commonly found in P. nigrum fruits. During postlab discussion, the students were encouraged to search for information about the biological properties of the putatively identified compounds. Most students found that piperine shows larvicidal activity. Thus, an experiment was conducted by a postgraduate research group to investigate the larvicidal potential of P. nigrum waste extracts. From the results, the students concluded that the hexane extract had higher larvicidal activity than the dichloromethane extract. We also provided students with the opportunity to identify piperine using (+)-APCI FT-ICR MS spectra. The proposed experiment helped students to learn and practice GC–MS and stimulated them to search the scientific literature for solutions to environmental problems.

Flowers from Dendranthema x grandiflorum (Ramat.) Kitam. are grown in Brazil for floristic trade, and residues from different cultivars are generated, containing flowers, leaves and stems. These residues can be used to produce larvicidal products. To confirm this hypothesis, 27 dichloromethane extracts were produced from Dendranthema x grandiflorum agricultural residues. All were analyzed by GC–MS and FT-ICR MS with two different ionization sources, APCI and ESI. The spectra and chromatograms were converted to matrices, which were used as input for PCA analyses. Simultaneously, the extracts at concentrations of 5 and 15 ppm were submitted to larvicidal assays on Aedes aegypti larvae, the etiological agent of dengue, chikungunya and zika diseases. High larvicidal activity (larvae mortality > 80%) was found for 14 samples, medium larvicidal activity (70% > larvae mortality > 40%) for 4 samples and low larvicidal activity (larvae mortality

The chemical composition and biological properties of citronella essential oil were modified by enzymatic esterification reaction of the major monoterpenic alcohols with cinnamic acid. The almost complete conversion of geraniol and citronellol present in the citronella (Cymbopogon winterianus) essential oil, into geranyl (99%) and citronellyl (98%) cinnamates was obtained after 48 hours of reaction using a molar ratio of 3:1 (cinnamic acid/alcohol), lipase concentration (Novozym 435) of 15% (w/w) and 70 °C. The esterified oil showed higher antimicrobial activity against Staphylococcus aureus bacteria resistant to oxacillin and penicillin and also greater larvicidal activity against Aedes aegypti larvae compared to unesterified oil. The results concerning the evaluation of toxicity against Artemia salina and cytotoxicity against monkey kidney epithelial cells also showed the superiority of the esterified oil.

Residues of the chrysanthemum agroindustry from different cultivars of Dendranthema x grandiflorum are sold in the Vitoria (Espirito Santo State, Brazil) marketplaces. Because of the large of varieties of this hybrid species, this study aimed to confirm the chemical similarity of the residual material collected in one year at the commercial places in neighborhoods of the city (Vitoria) for using it as an homogenous raw material to prepare larvicidal products. Dichloromethane and methanol extracts were produced from 27 samples. Medium infrared (MIR) spectra were obtained in triplicate for the 54 extracts. MIR data were analyzed by principal components analysis (PCA), which divided the samples into two groups (GA1 and GA2) for dichloromethane extracts and into four groups (GB1, GB2, GB3 and GB4) for methanol extracts. The methanol extracts, we could see clear separation among the groups based on their classes of substances. The dichloromethane ones, it was possible to identify separation between GA1 and GA2 by classes of triterpene esters and diacylglycerols based on their mass peak intensities. Mixtures obtained from dichloromethane extracts (FA) and methanol extracts (FB) were assayed on Aedes aegypti larvae at the concentration 15 ppm. FB mixtures no larval mortality was observed, but FA mixtures were 100% active, possibly by the presence of fatty acids, triterpenes, steroids and alkamides in the samples of this group. These results show that residues of different varieties of the hybrid Dendranthema x grandiflorum generate chemically similar extracts, particularly for the lipophilic ones (FA), which can be used as a homogeneous raw material to obtain biologically active products, notably larvicides products.

Endothelial dysfunction in obesity plays a key role in the development of cardiovascular diseases, and it is characterized by increased vascular tonus and oxidative stress. Thus, this study aimed to investigate the vasodilatory and antioxidant activities of Mandevilla moricandiana ethyl acetate fraction and subfractions. Vascular effects were investigated on aorta isolated from control and monosodium glutamate (MSG) induced-obese Wistar rats, and antioxidant activity was assessed by 2,2-diphenyl-1-picrylhydrazyl (DPPH) and oxygen radical absorbance capacity (ORAC) methods. The ethyl acetate fraction (MMEAF) induced a concentration-dependent vasodilation on aortic rings through the NO pathway, with the involvement of histamine H1 and estrogen ERα receptors and showed potent antioxidant activity. In aorta of MSG obese rats, maximal relaxation to acetylcholine was increased in the presence of MMEAF (3 µg/mL), indicating that MMEAF ameliorated obesity-induced endothelial dysfunction. Quercetin and kaempferol aglycones and their correspondent glycosides, as well as caffeoylquinic acid derivatives, A-type procyanidin trimer, ursolic and oleanolic triterpenoid acids were identified in subfractions from MMEAF and seem to be the metabolites responsible for the vascular and antioxidant activities of this fraction.

Glycosylated flavonoids, caffeoylquinic acid and 3,5-dicaffeoylquinic acid have been identified in the ethyl acetate partition from the crude ethanol extract of Tocoyena bullata (Rubiaceae) leaves. The fraction containing the mixture of flavonol rutin and a tetraglycosylated flavonoid showed 89.2% inhibition and the mixture of isoquercitrin and 3,5-dicaffeoylquinic acid showed 88.5% inhibition of mast cell degranulation. These results demonstrated that the tetraglycosylated flavonoid, rutin, isoquercitrin and 3,5-dicaffeioylquinic acid were the most promising phenolics for inhibition of mast cell degranulation. For the first time the identification of phenolic constituents and their correlation with inhibitory effect on mast cell degranulation were reported in this work

The specie Ocotea notata (Nees & Mart). Mez is a tree with 5 meters high, that can be found in restinga regions in the Brazilian coast. This study describes a phytochemical investigation, total phenolic content and the antioxidant activity of extracts and fractions by DPPH and ORAC. Phenolic content revealed equivalent concentration between evaluated samples, similar to found in the leave extract (66.4 mEq GA/g). By DPPH, extracts and fractions showed effective concentration (EC50) lower than the standards Ginkgo biloba 761® (23.60 ± 0.64 µg/ml) and quercetin (6.06 ± 0, 92 µg/mL); for the ORAC method, ethyl acetate partition showed a value of 2.06 mmol Trolox equivalent g−1 better than obtained in Ginkgo biloba (1.03 ± 0.25 mmol.Trolox equivalent g−1. The butanol partition (0.52 mmol.Trolox equivalent g−1) and the aqueous residue (0.74 mmol Trolox equivalent g−1) have a lesser ORAC potential than ethyl acetate partition. The butanolic partition, investigated by LC-DAD-MS/MS and QTOF-MS, revealed six major compounds: miquelianin (1), isoquercitrin (2), quercitrin (3), kaempferol-3-O-pentose (4), afzelin (5) and isorhamnetin-glucuronide (6).

In vitro conservation of Mandevilla moricandiana was performed by slow-growth storage and encapsulation–dehydration. For slow-growth storage, half- and full-strength Murashige and Skoog (MS) medium and Woody Plant Medium, with or without sorbitol, mannitol, or glucose, were used to test the development of nodal segments and maintenance of plant viability after 6 mo. Recovery was performed using MS medium. The basal medium and carbon source did not interact, and only the carbon source had a significant effect on slow-growth storage and recovery. Sorbitol and glucose, individually or in combination, promoted development of plants with a low multiplication rate during the slow-growth period and a high multiplication rate during the recovery period. For encapsulation–dehydration, nonencapsulated and sodium alginate-encapsulated nodal segments were evaluated to determine their viability after storage at different temperatures. Nonencapsulated nodal segments gave 16.6% recovery after 60 d at 25°C. The effects of preculturing encapsulated nodal segments in MS medium with 0.4 or 0.75 M sucrose followed by dehydration were also tested. Capsules precultured for 48 h in the presence of 0.40 M sucrose and dehydrated to 40% moisture content showed 93.3% recovery. These conditions were then used to store capsules under different temperatures and for different lengths of time. The precultured capsules showed ca. 30% recovery after storage for 30 d at 4°C. Well-developed plantlets regenerated from encapsulated, stored nodal segments were rooted and acclimatized successfully, with 100% survival.

Ethanol extracts obtained from Schinus terebinthifolius Raddi fruits and leaves were active against Escherichia coli with MIC of 78 μg mL−1 for both extracts. Phytochemical analyses revealed a major presence of phenolic acids, tannins, fatty acids and acid triterpenes in the leaves and phenolic acids, fatty acids, acid triterpenes and biflavonoids in the fruits. Major compounds isolated from the plant, such as the acid triterpene schinol, the phenolic acid derivative ethyl gallate and the biflavonoids agathisflavone and tetrahydroamentoflavone, showed very little activity against E. coli. Bioautography of the ethanol extracts on silica gel plate showed inhibition zones for E. coli. They were removed from the plate and the compounds identified as a mixture of myristic, pentadecanoic, palmitic, heptadecanoic, stearic, nonadecanoic, eicosanoic, heneicosanoic and behenic fatty acids.

Ethanol extract obtained from dried leaves of Acmella oleracea afforded after a liquid/liquid partition procedure a larvicidal hexane fraction (LC50 = 145.6 ppm) and a non larvicidal dichloromethane one. From the inactive fraction, three amides were identified, two new structures, named deca-6,9-dihydroxy-(2E,7E)-dienoic acid isobutylamide (1), deca-8,9-dihydroxy-(2E,6Z)-dienoic acid isobutylamide (2) and the known nona-2,3-dihydroxy-6,8-diynoic acid 2-phenylethylamide (3). Bioassay-guided chromatographic fractionation of the hexane partition led to the identification of an amide mixture, nona-(2Z)-en-6,8-diynoic acid 2-phenylethylamide (4) and deca-(2Z)-en-6,8-diynoic acid 2-phenylethlylamide (5). This mixture was active against Aedes aegypti larvae at LC50 = 7.6 ppm. Low toxicity of crude extracts and derived fractions on Artemia salina nauplies showed the possibility of using them to control the A. aegypti mosquito larvae. This is the first report on larvicidal activity of acetylenic 2-phenylethylamides and their identification in A. oleracea leaves.

In hybrid cultivated form, Dendranthema grandiflorum (Ramat.) Kitam., Asteraceae, flowers (Chrysanthemum morifolium Ramat.) were utilized in the production of extracts, which were analyzed for larvicidal activity against Aedes aegypti third instar larvae. Methanol and dichloromethane extracts showed LC50 values of 5.02 and 5.93 ppm, respectively. Using GC–MS, phytochemical analyses of the dichloromethane extract showed the presence of triterpenoids and fatty acids, while flavonoids and caffeoylquinic acids were shown to occur in the methanol extract by ESI Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FT-ICR-MS). Triterpenoids and fatty acids are well known insecticidal compounds. From this study, it can be concluded that D. grandiflorum grown for floriculture, as an agribusiness, can have additional applications as raw material for the production of insecticidal products. Keywords: Aedes aegypti, Caffeoylquinic acids, Agribusiness, Fatty acids, Larvicidal activity, Triterpenoids

The allelopathic potential of Terminalia catappa L. Combretaceae fruits and leaves on Lactuca sativa L. (lettuce), Euphorbia heterophylla L. and Commelina benghalensis L. was studied. Bioassays indicated the highest activity for dichloromethane and ethyl-acetate fractions of ethanolic extracts from fruits, and the mean effective concentration (EC50) was determined. 2-Pentadecanone; vanillic, siringic, ferulic, p-coumaric, palmitic and stearic acids were characterized in the dichloromethane fraction, and 3,4,4′-tri-O-methyl ellagic acid and β-sitosterol-3-O-β- d -glucoside were isolated from it. No allelopathic effects were observed when the dichloromethane extracts of T. catappa fruit or leaf extracts were applied to the weeds E. heterophylla and C. benghalensis. Bioassays with seasonal sampling revealed an influence on the allelochemical potential of T. catappa. Considering the methodology adopted and the experimental results, the allelopathic activity of T. catappa seems to be related to the interaction of different groups of substances, some of them identified and characterized in this work.

This work describes the phytochemical study of the methanol extract obtained from leaves of Guarea macrophylla, leading to the isolation and identification of three flavonoid glycosides (quercetin 3-O-β-D-glucopyranoside, quercetin 3-O-b-D-galactopyranoside, kaempferol 7-O-β-D-glucopyranoside) and a neolignan glucoside, dehydrodiconiferyl alcohol-4-β-D-glucoside. All compounds were identified by a combination of spectroscopic methods (¹H, 1D, 2D NMR, 13C and UV), ESI-MS and comparison with the literature data. This is the first report of flavonoids in the genus Guarea and of a neolignan glucoside in the Meliaceae family.

In models of metabolic disorders, cinnamon improves glucose and lipid metabolism. This study explores the effect of chronic supplementation with aqueous cinnamon extract (CE) on the lipid metabolism of rats. Male adult Wistar rats were separated into a control group (CTR) receiving water and a CE Group receiving aqueous cinnamon extract (400 mg of cinnamon per kg body mass per day) by gavage for 25 consecutive days. Cinnamon supplementation did not change the food intake or the serum lipid profile but promoted the following changes: lower body mass gain (P = 0.008), lower relative mass of white adipose tissue (WAT) compartments (P = 0.045) and higher protein content (percentage of the carcass) (P = 0.049). The CE group showed lower leptin mRNA expression in the WAT (P = 0.0017) and an important tendency for reduced serum leptin levels (P = 0.059). Cinnamon supplementation induced lower mRNA expression of SREBP1c (sterol regulatory element-binding protein 1c) in the WAT (P = 0.001) and liver (P = 0.013) and lower mRNA expression of SREBP2 (P = 0.002), HMGCoA reductase (3-hydroxy-3-methylglutaryl-CoA reductase) (P = 0.0003), ACAT1 (acetyl-CoA acetyltransferase 1) (P = 0.032) and DGAT2 (diacylglycerol O-acyltransferase 2) (P = 0.03) in the liver. These changes could be associated with the reduced esterified cholesterol and triacylglycerol content detected in this tissue. Our results suggest that chronic ingestion of aqueous cinnamon extract attenuates lipogenic processes, regulating the expression of key enzymes and transcriptional factors and their target genes, which are directly involved in lipogenesis. These molecular changes possibly promote adaptations that would prevent an increase in circulating cholesterol and triacylglycerol levels and prevent lipid accumulation in tissues, such as liver and WAT. Therefore, we speculate that cinnamon may also be useful for preventing or retarding the development of lipid disorders.

The bioassay-guided fractionation of the hexane extract obtained from the medicinal plant Myroxylon balsamum (red oil) was conducted in preparative thin layer chromatography on silica gel. The obtained fractions and some terpenoids and phenylpropanoids were assayed as larvicidal on third instar Aedes aegypti larvae, NPPN colony. The results indicate that the sesquiterpene nerolidol was the active constituent in the extract and that the sesquiterpenes were more active than the monoterpenes and phenylpropanoids utilized in this study. Lipophilicity seems to be an important property for the activity since the compounds with hydroxyl, carbonyl and methoxyl groups were less active. The results confirm also that essential oils can be a good tool for the control of dengue.

Mandevilla guanabarica is an endemic plant from Brazil, with pharmacological and ornamental potential, both unexplored. This study established the best culture medium for in vitro plant maintenance, efficient protocol for its regeneration, and callogenesis from different explants excised from in vitro-grown plants. Woody plant medium with double boron concentration (WPM B) plus 2.27 µM thidiazuron or 0.49 µM 2-isopentenyladenine provided multiplication rates higher than 1:6. Shoots were 100% rooted on WPM B. After acclimatization, plants showed 83% survival. For callogenesis, the use of MS media supplemented with high concentrations of picloram or 2,4-dichlorophenoxyacetic acid produced, respectively, friable or compact non-morphogenic calluses from different types of explants. This micropropagation protocol allows the production of seedlings of M. guanabarica for ornamental or commercial uses, and for conservation purposes; calluses can be used to establish suspension cultures in prospecting for bioactive compounds.

Fractionation of Piper nigrum ethanol extract, biomonitored by assays on pyrethroid-resistant Aedes aegypti larvae yielded isolation of the larvicidal amides piperolein-A and piperine. Comparing LC50 values, the ethanol extract (0. 98 ppm) was the most toxic, followed by piperolein-A (1. 46ppm) and piperine (1. 53ppm). O fracionamento do extrato etanólico de Piper nigrum biomonitorado por ensaios em larvas de Aedes aegypti resistentes a piretróides resultou no isolamento das amidas larvicidas piperoleína-A e piperina. Comparando-se os valores de CL50, o extrato etanólico (0. 98ppm) foi o mais tóxico, seguido pela piperoleína-A (1. 46ppm) e piperina (1. 53ppm).

The chemistry and pharmacology of species of the family Monimiaceae are reviewed, with special attention given to the genera Mollinedia and Siparuna, the two most important and representative in Brazil. The isolation of benzylisoquinoline alkaloids and kaempferol derivatives from Siparuna apiosyce is reported, as well as the isolation of aporphines from the fruits of Siparuna arianeae. Cinnamic acid derivatives and a gamma-lactone were isolated from Mollinedia gilgiana and Mollinedia marliae.

The fruits of Pilosocereus arrabidae (Cactaceae) is found in the Grumari shoal, located in the Rio de Janeiro state, Brazil and, several studies have already highlighted the importance of consuming its fruits. This work aims to investigate the physical, mineral and physicochemical properties of its fruits as well as to establish the knowledge about their chemical constituents and antioxidant properties. The peel (Pe) and pulp (Pu) extracts were obtained by maceration with the following solvents: hexane (HX), dichloromethane (DCL), ethyl acetate (EAC) and ethanol 70% (ET). The extracts were analyzed by Gas Chromatography coupled to Mass Spectrometry (GC–MS) and, by High Performance Liquid Chromatography (HPLC–DAD and HPLC–MS) for its chemical investigation. For the antioxidant activity investigations the ORAC, DPPH and ferrous ion chelating capacity (FICC) tests were performed. As results, we found higher yields for peels (72%) compared to pulps (28%). By the physical–chemical analyses we point out the fruits as a good source of fiber (pulp: 6.01 mg/100 g; peel: 8.02 mg/100 g). The minerals were analyzed by the method of issuing flames and indicated high levels of selenium (DRI for pulp and peel: 147%) and manganese (DRI pulp: 97.69% and DRI peel: 269.56%). The total flavonoid contents of the fruits performed by HPLC–DAD presented 0.45 μg equiv. in quercetin/mL of peel EAC extract and 0.25 μg equiv. in rutin/mL of pulp EAC extract. The antioxidant activities by the ORAC, FICC and DPPH methods indicated that the ET extracts showed antioxidant activities above the standards adopted for the tests. Among these, we highlight the ET extract of the pulp with EC 50 of 17.57 ± 0.27 μg/mL, lower than Ginkgo biloba EGB761® (23.40 ± 0.04 mg/mL). By the FICC test the EAC extract of the peel and pulp showed 70.0% and 53.4% activity, respectively, at 500 mg/mL, higher than the standard quercetin (50.0%). By the HPLC–DAD and HPLC–MS methods there were detected, for the first time on this species, the presence of the following flavonoids on the EAC extracts: quercetin, rutin, catechin, dihydrokaempferol, quercetin 3 or 4′-O-glucoside, kaempferol and isorhamnetin. By the GC–MS analysis there were detected on the DCL extracts saturated fatty acids (palmitic and stearic) and, on the HX extracts, methylated sugars (peel) and menthol (pulp). To sum up, the fruits of P. arrabidae display antioxidant potential correlated to flavonoid presence, and, high levels of selenium, manganese and fibers, characteristics that can promote beneficial effects on human health.

The chemical composition of volatile compounds in leaves of Mandevilla guanabarica from three restingas in Rio de Janeiro was characterized by GC/MS after SDE. The volatiles common were 3-hexen-1-ol, β-caryophyllene and germacrene D, which were majority compounds for plants from Grumari, Jurubatiba and Marica, respectively. M. guanabarica also contained other compounds: α-cubebene, α-copaene and cubebene (Grumari); β-ocimene, α-caryophyllene and germacrene B (Jurubatiba); and β-elemene and alloaromadendrene (Marica). Although some compounds were common to all locations, the qualitative and quantitative chemical profiles of volatile compounds of M. guanabarica from three different areas in the same season, with similar conditions of temperature and precipitation, were distinct. Leaf histochemical analysis revealed the presence of fatty acids in idioblasts, and rubber grains and droplets of lipophilic substances in the mesophyll, for all three samples. These results indicate the possible influence of physiological variations and/or environmental conditions on the composition of volatiles in M. guanabarica .