Abstract Phytochemical studies of Cespedesia spathulata (Ochnaceae) leaves using 1H, 13C NMR, and GC-MS have led to the isolation of some metabolites identified for the first time in these species such as cathechin, epicatechin, vitexin, orientin, 6’’-O-acetyl-vitexin, sitosterol, stigmasterol, phytol, 4,5-dihydrovomifoliol and a mixture of aliphatic methyl esters, together with ochnaflavone, which was previously isolated from this plant. The modulating activity of some fractions and compounds from Cespedesia spathulata towards tyrosinase enzyme was assayed by spectroscopic and theoretical means/experiments. The dichloromethane fraction (133 μg mL-1) and ochnaflavone (333 μM) inhibited tyrosinase activity by 20 % and 2.0 %, respectively, whereas the ethyl acetate fraction (666 μg mL-1) and ±catechins (catechin and epicatechin - 800 μM) activated it by 104 % and 384 %, respectively. Quantum chemical calculations suggested that catechin and epicatechin are better activators than L-DOPA by interacting with Cu (II) ions. Molecular docking results suggested that hydrogen bonding and hydrophobic interactions are the main binding forces between each tyrosinase activator and the amino acid residues inside the active protein binding pocket.

FMOC-Cl is a derivatizing agent widely used both in N-protection reactions of α-amino acids as well as in quantification and detection of amino acids and related molecules using HPLC-PDA or fluorescence analysis. In this work we studied the reaction of FMOC-Cl with gabapentin. However, it was observed that the degradation of gabapentin-N-FMOC and FMOC-Cl to FMOC-OH occur simultaneously in presence of the basic reaction medium which is specific for gabapentin derivatization. The degradation reaction is accelerated in temperatures above 45 °C and also by the time of contact of the reactant and product with basic medium. In this study, gabapentin derivatization reactions were shown to be cleaner and more efficient when an FMOC-Cl/gabapentin ratio of 2:1 was used, at 25 °C over a period of 15 minutes.

Abstract The cultivation of aromatic species to obtain essential oils has great economic importance, presenting an increasing demand from different industrial sectors, especially to menthol mint (Mentha arvensis L.) essential oil, rich in menthol (70-80%). Consortium cultivation has been an important practice in agricultural systems whose land use is necessary, consequently promoting strong competition for light in reduced space. Thus, this study aimed verifying if different light intensities might promote chemical, metabolical and anatomical alterations in menthol mint. Plants were grown in greenhouse at different average of light intensities (137, 254, 406 and 543 µmol photons m2 s1). Samples were collected 43 days after germination and submitted to following analyses: Gravimetric test, photosynthetic pigments, soluble fractions, enzymatic activity, N-total, trichome density and histochemistry and chemometric test based on essential oil chemical profile. Fresh mass gain, trichome density, essential oil content and soluble sugars were positively influenced by light intensity increase. On the other hand, total-N, NO3−-N and pigments content have decreased influenced by light intensity increase. In the secretion from the trichomes, phenolic substances were reported, as well as lipophilic ones in the peltate ones. The increase of oxygenated monoterpenes was favored by light intensity decrease.

Fifty-two samples of street cocaine seized in the state of Rio de Janeiro, from May 2016 to April 2017, were evaluated according to their purity, presence of inorganic and sugar diluents and concentration of pharmacologically active adulterants. Cocaine contents, as well as the adulterants caffeine, lidocaine and phenacetin, were evaluated by gas chromatography coupled with mass spectrometry. The samples were screened by Raman spectroscopy for the presence of inorganic diluents and carbohydrates. The main diluents were calcium carbonate and sodium bicarbonate, which were found in 93% and 71% of the cocaine hydrochloride samples, respectively. Caffeine was found in 91% of the cocaine hydrochloride samples, while phenacetin was found in all freebase cocaine samples. Freebase cocaine samples were majorly composed of pharmacological active compounds (adulterants), unlike cocaine hydrochloride samples, which were majorly composed of inorganic compounds (diluents). It could be observed, by Raman Spectroscopy associated to multivariate analysis, similarities on cocaine hydrochloride composition according to certain criminal gangs. The percentage of pharmacological active compounds varied significantly on the analyzed samples, showing that these adulterants are indiscriminately added to street cocaine, what may increase consumers’ health risks.

Abstract: This study aims to identify phenolic compounds in dichloromethane and methanolic extracts of the rhizome of Renealmia nicolaioides collected in the North Region of Brazil. Two known diarylheptanoids, 1,7-bis(4-hydroxyphenyl)-(1E)-1-hepten-3-one (1), and 5R-1,7-bis(4-hydroxyphenyl)-1E-hepten-5-ol (2), and a new one (1R,2S,5S)-2-hydroxy-1,7(p-hydroxyphenyl)-centrolobine (3), as well as one flavonoid, 3-metoxi-quercetin (4) were isolated by chromatographic procedure and identified by spectroscopic techniques (1H and13C NMR, HRMS and CD). The acetyl derivative of 2 was used to confirm its structure. All four compounds are reported for the first time for this genus, and this is the first occurrence of compound 1 as a natural metabolite. The results reported here are unprecedented for the genus Renealmia.

ABSTRACT This study aims to identify special metabolites in polar extracts from Urochloa humidicola (synonym Brachiaria humidicola) that have allelopathic effects and induce secondary photosensitization in ruminants. The compounds were isolated and identified via chromatographic and spectroscopic techniques. The compounds 4-hydroxy-3-methoxy-benzoic acid, trans-4-hydroxycinnamic acid, and p-hydroxy-benzoic acid; the flavonols isorhamnetin-3-O-β-d-glucopyranoside and methyl quercetin-3-O-β-d-glucuronate; and kaempferitrin, quercetin-3-O-α-l-rhamnopyranoside, and tricin were identified in the extract from the leaves of Urochloa humidicola. Two furostanic saponins, namely, dioscin and 3-O-α-l-rhamnopyranosyl-(1-4)-[α-l-rhamnopyranosyl-(1-2)]-β-d-glucopyranosyl-penogenin, as well as catechin-7-O-β-d-glucopyranoside were identified in the methanolic extract obtained from the roots of this plant. This species features a range of metabolites that may be toxic for animals if used in food and may interfere with the growth medium, thereby inhibiting the development of other species.

ABSTRACT The objective of this study was to identify thyroid hormones and to examine their putative site of synthesis in Achatina fulica snails. For this purpose, radioimmunoassays were performed for T3 and T4 before and after long starvation with or without hemolymph deproteinization. Sodium/iodide symporter activity in vivo was analyzed through 125I administration with and without KClO4 pretreatment. Only T4 was detected, and its concentration decreased due to starvation or deproteinization. However, high-performance liquid chromatography analysis also showed the presence of T2 and T3 apart from T4, but rT3 was not detected in the A. fulica hemolymph. The sodium/iodide symporter activity was greater in cerebral ganglia than digestive gland, but KClO4 treatment did not inhibit iodide uptake in any of the tissues analyzed. Altogether, our data confirm for the first time the presence of thyroid hormones in A. fulica snails and suggest their participation in the metabolism control in this species, although the putative site of hormone biosynthesis remains to be elucidated.

In this work were determined the total phenolic contents, antioxidant activity and chemical composition of twelve samples of green propolis acquired from beekeepers and other twelve commercial extracts samples from different regions of Southeast Brazil. The phenolic contents and the antioxidant activity were evaluated by the Folin-Ciocalteau and DPPH, ABTS and FRAP methods, respectively. Both types of propolis showed significant radical scavenging properties. HPLC-PDA was applied for quantification of chlorogenic acid, caffeic acid, ferulic acid, para-coumaric acid, rosmarinic acid, vanillin, hesperidin, naringenin, pinobanksin, kaempferol, Artepillin-C (4-hydroxy-3,5-diprenyl cinnamic acid), kampheride and pinostrobin. Despite the chemical composition of both in natura and commercial propolis extracts were similar the multivariate analysis allowed the discrimination between them.

The phytochemical investigation of Clusia lanceolata leaves yielded fourteen compounds including six flavones, vitexin, isovitexin, isovitexin-2"-O-α-L-rhamnopyranoside, vitexin-2"-O-α-L-rhamnopyranoside, orientin and isoorientin, two phaeophytins [132-hydroxy-(132-S-)-phaeophytin a and 132-hydroxy-(132-R)-phaeophytin a], two triterpenes, α- and β-amyrin, and four steroids, β-sitosterol, stigmasterol, sitosterone and stigmasterone. Their structures were assigned based on spectroscopic analysis, including two-dimensional NMR techniques and comparison with literature data. The antioxidant capacity in vivo of vitexin and mixing isovitexin-2"-O-α-L-rhamnopyranoside and vitexin-2"-O-α-L-rhamnopyranoside was evaluated using the yeast Saccharomyces cerevisiae as the biological system model and hydrogen peroxide as a stressor agent. The results showed that the tested flavonoids were able to protect the yeast cell against the oxidative damage caused by H2O2.

<p>GC-FID, GC-MS and NMR spectral data were used to analyze the composition of the essential oils extracted from young and mature leaves of <italic>E. uniflora</italic> L. grown in Seropédica - RJ. Thirty and twenty-five compounds were identified, corresponding to approximately 98.19% and 93.77% of the total amount of oils, respectively. The major components of the young leaves were (3<italic>Z</italic>,7<italic>E</italic>)-3,7-dimethyl-10-(propan-2-ylidene)cyclodeca-3,7-dienone (germacrone, 34.59%), 4,5,6,7-tetrahydro-3,6-dimethyl-5-(prop-1-en-2-yl)-6-vinylbenzofuran (curzerene, 26.56%) and (1<italic>Z</italic>,5<italic>E</italic>)-1,5-dimethyl-8-(propan-2-ylidene)cyclodeca-1,5-diene (germacrene B, 12.72%), and of the mature leaves were curzerene (35.75%), germacrene B (19.22%) and β-(<italic>E</italic>,1<italic>R</italic>,9<italic>S</italic>)-4,11,11-trimethyl-8-methylenebicyclo[7.2.0]undec-4-ene (caryophyllene, 12.55%). The multivariate analysis applied to data from GC-MS allowed discrimination of the differences in the chemical composition of oils based on the age of the leaves. The components germacrone, curzerene e furanodiene (not observed during conventional chromatographic analysis) were isolated from the essential oil of young leaves. These compounds were characterized by GC-MS, and ¹H and ¹³C NMR (1D and 2D).</p>

Essential oils of galled and non-galled leaves of Clusia lanceolataCambess., Clusiaceae, were obtained by hydrodistillation and analyzed by GC and GC/MS. The chemical composition of both oils was similar, with a predominance of sesquiterpene caryophyllenes. The extracts from the leaves were evaluated regarding total phenols, flavonoids and proanthocyanidins. Galled leaves showed higher levels of phenolics and proanthocyanidins, since the content of flavonoids was higher in non-galled leaves. The chromatographic profiles of extracts were obtained by using HPLC/DAD and LC-ESI-MS. Electrospray ionisation (ESI) in positive and negative ion mode was used to identify four flavones C-glycosides in both extracts. The study constitutes a first report on the chemical research of C. lanceolata.The extract from galled leaves had a higher antioxidant activity.

The antioxidant activities and polyphenolic levels of "assa peixe," "cambara," and "morrão de candeia" Brazilian honeys were investigated. Phenolic extracts of 11 honeys were evaluated spectrophotometrically to determine their total phenolic and flavonoid contents, and their antioxidant activities were measured using DPPH, ABTS, and FRAP assays. High-performance liquid chromatography coupled with diode array detection was applied to determine the phenolic composition of the honey extracts. The presence of fourteen phenolic compounds was established (eleven phenolic acids and three flavonoids), as well as HMF and abscisic acid. Principal component analysis was applied to classify the honey samples according to their floral origins.

Foram avaliadas as atividades antioxidantes e o conteúdo de polifenóis de cinco méis silvestres e quatro de laranjeira, bem como de seus extratos fenólicos. A identificação e quantificação das substâncias fenólicas foram realizadas por HPLC-DAD (cromatografia líquida de alta eficiência com detecção por arranjo de diodos). A atividade sequestradora de radicais livres, determinada por 2,2-difenil-1-picrilhidrazil (DPPH•) e expressa como CE50, variou de 10,81 a 52,64 mg mL-1 para mel e de 6,17 a 52,87 mg mL-1 para extrato. A atividade antioxidante dos extratos foi também determinada pelos métodos com 2,2'-azinobis-(3-etil-benzotiazolino-6-ácido sulfônico) sal diamônio (ABTS) e poder antioxidante de redução do ferro (FRAP), e os resultados variaram de 46,53 a 383,49 mmol TE 100 g-1 e de 34,99 a 408,14 mol Fe(II) 100 g-1, respectivamente. Também foram avaliados os teores de fenóis totais e flavonóides pelos métodos de Folin-Denis e complexação com cloreto de alumínio, respectivamente. A atividade antioxidante e o teor de fenóis totais mostraram-se altamente correlacionáveis.

The antioxidant activities and total polyphenolic content of five multifloral and four orange blossom Brazilian honey samples and their phenolic extracts were investigated. Identification and quantification of phenolic compounds were carried out by HPLC-DAD (high-performance liquid chromatography with diode-array detection). The radical scavenging activities, determined with 2,2-diphenyl-1-picrylhydrazyl (DPPH•) and expressed as EC50, ranged from 10.81 to 52.64 mg mL-1 for honey and 6.17 to 52.87 mg mL-1 for the extracts. The extract antioxidant activities were also determined by 2,2'-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) and ferric reducing antioxidant power (FRAP) assays, and the results varied from 46.53 to 383.49 mmol TE 100 g-1 and 34.99 to 408.14 mol Fe(II) 100 g-1, respectively. It was also evaluated the total phenolic and flavonoid contents by the Folin-Denis and aluminum chloride methods, respectively. Antioxidant activities and total phenolic contents were found to be highly correlated.

Um mecanismo alternativo para a indução assimétrica 1,4, na adição estereosseletiva da (R)-pantolactona ao 2-fenilpropilceteno foi investigado teoricamente. Um mecanismo envolvendo uma transferência de hidrogênio intermolecular foi proposto, que considera a participação ativa da dimetiletilamina e seu íon como agentes de transferência de hidrogênio. No primeiro passo, uma molécula de dimetiletilamina neutra interage com o anel de 7 membros do enol intermediário. Uma interação ácido-base específica é estabelecida entre o grupo hidroxila do enol e o átomo de nitrogênio da amina. A amina neutra é básica o suficiente para remover o hidrogênio. Uma outra molécula de amina protonada doa seu hidrogênio à ligação dupla C=C, para fornecer os produtos desejados. A estereoquímica foi definida pelo modo como as moléculas de amina neutra e protonada aproximam-se do enol. O excesso diasteroisomérico encontrado concorda com o dado experimental [para (S, R) e (R, R) é de 99:1].

An alternative mechanism for the 1,4-assymmetric induction in the stereoselective addition of (R)-pantolactone to 2-phenylpropylketene was theoretically investigated. A mechanism involving an intermolecular proton transfer assisted by two amine molecules was proposed, which considered the active participation of the dimethylethylamine and its ion as proton transfer agents. In the first step, a neutral dimethylethylamine interacts with the seven-membered ring of the enol intermediate. A specific acid-base interaction is established between the hydroxyl group of the enol and the nitrogen atom of the dimethylethylamine. The neutral dimethylethylamine is basic enough to remove the proton. Another protonated dimethylethylamine is considered to donate its proton to the C=C double bond to give the desired products. The stereochemical outcome was defined by the way that the neutral and protonated dimethylethylamine approached to the enol. The diastereoisomeric ratio found is in good agreement with experiments [for (S, R) and (R, R) it is 99:1].

O alil-benzeno natural safrol, isolado do óleo de Sassafraz (Ocotea pretiosa, Benth) foi utilizado como matéria-prima na síntese de um novo análogo aromático do estrigol que é um potente estimulante de germinação. O novo análogo foi obtido como uma mistura de epímeros em C2' que foram quantificados e separados por cromatografia líquida de alta eficiência.

Safrole, isolated from Sassafraz Oil (Ocotea pretiosa, Benth), has been used as starting material in the synthesis of a new strigol analogue which is active as germination stimulant. The new analogue was obtained as a mixture of epimers at C2' which could be separated by high-performance liquid chromatography.