The inhibitory action of three imine-chalcones on carbon steel corrosion in HCl was investigated by theoretical and experimental methods. Quantum descriptors were calculated at the conductor-like polarizable continuum model (CPCM)-Becke-3 Parameter-Lee-Yang-Parr (B3LYP)-D3/def2-TZVPP level allowing the prediction of efficiency inhibition ranking. Electrochemical techniques and mass loss experiments were employed to determine inhibition efficiencies and related experimental parameters. Scanning electron microscopy was employed for metal surface analysis. The N-[(1Z,2E)-1,3-diphenylprop-2-in-1-ylidene]-1-phenethylamine (IM-F) was pointed out as the most efficient inhibitor in this group, with 96% of corrosion inhibition. Moreover, theoretical results obtained from periodic calculations for the adsorption on the Fe(110) surface corroborated the highest efficacy of IM-F.

A series of 2-amino-1,4-naphthoquinone derivatives (NQA-NQF) was synthesized by alternative methods (ultrasonication and microwave irradiation), with yields ranging from 40 to 71%, and without the need of further recrystallization. Each compound was evaluated against four Gram-positive (Bacillus subtilis, Enterococcus faecalis, Staphylococcus aureus and Bacillus cereus) and five Gram-negative (Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Acinetobacter baumannii and Klebsiella pneumoniae positive β-lactamase) bacteria strains. The NQF was the most active amino-naphthoquinone derivative with minimum inhibitory concentration (MIC) of 31.2 µg mL-1 against K. pneumoniae positive β-lactamase (a common intestinal bacteria which can cause life-threatening infections). On the other hand, NQA and NQC showed good activity as a potential antibiotic for the bacteria strains assayed, except for K. pneumoniae. In addition, the affinity of these three most active compounds (NQA, NQC, and NQF) for human serum albumin (HSA) was evaluated employing multiple spectroscopic techniques (steady-state, time-resolved, and synchronous fluorescence, as well as circular dichroism), combined with theoretical calculations (molecular docking). The interaction HSA:2-amino-1,4-naphthoquinones occurs spontaneously and moderately inside the subdomain IIA (Sudlow’s site I) via hydrogen bonding and van der Waals forces.

For this work, a hydroalcoholic extract was prepared from the aerial parts of the Malvaviscus arboreus (Malvaceae) species, popularly known as hibisco-colibri in Brazil; and then, investigated by infrared and NMR spectroscopy. A class of special metabolites containing a porphyrin skeleton and pyrrole units was determined by typical absorption spectra, mainly 1H and 13C NMR, thus indicating the capability of showing anti-corrosion effect. Therefore, the M. arboreus extract was examined as a corrosion inhibitor for AISI 1020 carbon steel in H2SO4 1 mol L-1, using a mass loss (gravimetric) technique. Results showed good corrosion inhibition efficiency, at both time and temperature variation. The maximum efficiency observed at 500 ppm was 97.5%, at 3 h, 24 h and 48 h. The surface morphology was analyzed by scanning electron microscopy (SEM), through which a higher homogeneity was observed in the presence of the M. arboreus extract. The hydroalcoholic extract of hibisco-colibri can be considered an efficient green agent for preventing corrosion.

In this work, two β-enaminoesters, EN1 and EN2, were synthesized, characterized and their anticorrosion effects on American Iron and Steel Institute (AISI) 1020 carbon steel in 0.5 mol L-1 HCl were investigated using gravimetric and electrochemical methods. The results revealed that both compounds inhibit corrosion. Good correlations were observed between results obtained for gravimetric and electrochemical methods. EN1 exhibited highest efficiency of 98% after 24 h of immersion in HCl solution. The adsorption of compounds on steel surface followed the modified Langmuir adsorption isotherm. Surface morphology of carbon steel was examined using scanning electron microscopy showing that the metal surface was protected by EN1 as inhibitor of corrosion.

A new series of 19-nor-clerodane diterpene derivatives was synthesized from the natural trans-dehydrocrotonin obtained from stem barks of Croton cajucara (Euphorbiaceae), a native medicinal plant of the Brazilian Amazon. The new derivatives were obtained by changes in the ketone moiety of trans-dehydrocrotonin leading to nitrogenated derivatives which are: three substituted hydrazine diterpenes, oxime, and methyloxime. The cytotoxic effect of the diterpene derivatives was evaluated by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay against Ehrlich carcinoma and K562 human leukemia cells. The cytotoxic activity of the hydrazine and oxime semi-synthetic derivatives was better than the one of the natural product trans-dehydrocrotonin. Moreover, all diterpenes were tested for their DNA topoisomerase I inhibitory activity, and the most effective one, in general, was observed to the phenyl-hydrazone derivative. Results indicated that the topoisomerase I inhibitory effect is correlated with the cytotoxic activity.

Polymers have received considerable attention for replacing synthetic inorganic and organic anti-corrosion inhibitors since they are not as toxic for the environment, besides being cheaper. Polyvinylpyrrolidone (PVP) has been studied due to its applicability, solubility, very low toxicity, cost and efficiency in corrosion inhibition against metals, such as zinc, aluminum, stainless steel, and others. Its anti-corrosion activity with 40000 g mol-1 was tested against AISI 1020 carbon steel in 0.5 mol L-1 HCl, and evaluated by electrochemical techniques: Potentiodynamic Polarization (PP), Linear Polarization Resistance (LPR), and Electrochemical Impedance Spectroscopy (EIS). The maximum efficiency was 90% and 89% in EIS and LPR, respectively, at concentration of 1.0 x 10-7 mol L-1. The adsorption mechanism was coherent with Langmuir isotherm model. The morphology of the corroding carbon steel surface, in the presence and absence of the PVP, was visualized using Scanning Electron Microscopy (SEM).

Os fungos micotoxigênicos podem comprometer a qualidade dos alimentos colocando em risco a saúde do homem e dos animais. As atividades antifúngicas de oito tiosemicarbazonas (1-8) e nove semicarbazonas (9-17) foram avaliadas frente Aspergillus flavus, A. nomius, A. ochraceus, A. parasiticus e Fusarium verticillioides. As tiosemicarbazonas apresentaram valores de MIC entre 125 a 500 µg/ml. As tiosemicarbazonas 1 e 2 exerceram atividade fungistática frente Aspergillus spp., e enquanto, a substância 2 apresentou atividade fungicida frente F. verticillioides. O composto 2 também foi capaz de apresentar efeito quelante (63%) frente ao ferro e, reduzir 28 e 71% o conteúdo de ergosterol de A. parasiticus nas concentrações de 31,2 e 62,5 µg/ml, respectivamente. Os resultados obtidos para a atividade antifúngica revelaram que a classe das tiossemicarbazonas foi mais ativa quando comparada a classe das semicarbazones e, a tiossemicarbazona 2 foi mais ativa frente Aspergillus spp.

Mycotoxigenic fungi can compromise the quality of food, exposing human and animal health at risk. The antifungal activity of eight thiosemicarbazones (1-8) and nine semicarbazones (9-17) was evaluated against Aspergillus flavus, A. nomius, A. ochraceus, A. parasiticus and Fusarium verticillioides. Thiosemicarbazones had MIC values of 125-500 µg/ml. The thiosemicarbazones 1 and 2 exerted fungistatic activity against Aspergillus spp., and thiosemicarbazone 2 exerted fungicidal activity against F. verticillioides. Compound 2 showed an iron chelating effect of 63%. The ergosterol content of A. parasiticus had a decrease of 28 and 71% for the 31.2 and 62.5 µg/ml concentrations of thiosemicarbazone 2 compared to the control. The obtained results of antifungal activity revealed that thiosemicarbazone class was more active when compared to semicarbazone class and, the thiosemicarbazone 2 was the most active compound, specially, against Aspergillus spp.

In this paper, thiosemicarbazones 4-N-cinnamoyl-thiosemicarbazone (CTSC), 4-N-(2'-methoxycinnamoyl)-thiosemicarbazone (MCTSC), and 4-N-(4'-hydroxy-3'-methoxybenzoyl)- thiosemicarbazone (HMBTSC) were solubilized in an oil-in-water (O/W) microemulsion system (ME_OCS), forming systems CTSC_ME_OCS, MCTSC_ME_OCS and HMBTSC_ME_OCS. The effectiveness of these systems in the process of inhibiting AISI 1020 carbon steel corrosion was evaluated in a saline solution (NaCl 0.5%), using a galvanostatic method. The tested thiosemicarbazones showed higher inhibitory effects (85.7% for CTSC_ME_OCS, 84.0% for MCTSC_ME_OCS, and 83.3% for HMBTSC_ME_OCS). The surfactant OCS (dissolved in H2O) and the ME_OCS system showed lower efficacies, with 71.0% for OCS and 74.0% for ME_OCS system.

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.

Uma nova e eficiente síntese de oito derivados da classe 1,3,4-tiadiazolio-2-fenilaminas (1-8, sendo o derivado 8 inédito na literatura) foi realizada utilizando cloreto de tionila ou cloreto de trimetilsilano como catalisadores sob irradiação de microondas ou ultra-som. Os compostos alvos foram obtidos em bons rendimentos e em tempo extraordinariamente curtos, 5 min sob irradiação de microondas e 10 min sob irradiação de ultra-som, quando comparados com a metodologia tradicional (24 a 48 h em repouso a temperatura ambiente). Os melhores rendimentos foram obtidos usando irradiação de microondas e, de maneira geral, usando o cloreto de tionila ao invés de cloreto de trimetilsilano. A citotoxicidade foi avaliada frente à linhagem de leucemia humana K562 e do linfoma Daudi, apresentando resultados promissores para o derivado cloreto de 4-fenil-5-(4'-nitro-estiril)-1,3,4-tiadiazolio-2-fenilamina.

A new and efficient synthesis of eight 1,3,4-thiadiazolium-2-phenylamine derivatives (1-8, where 8 is novel in the literature) was performed using thionyl chloride or trimethylsilyl chloride as catalysts under microwave or ultrasound irradiation. The target compounds were obtained in good yields and remarkably short times, 5 min under microwave irradiation and 10 min under ultrasound irradiation, where compared to traditional methodology (24 to 48 h at room temperature standing). The best yields were obtained using the microwave irradiation and, in general way, using thionyl chloride instead trimethylsilyl chloride. The cytotoxicity against K562 human leukemia and Daudi lymphoma lines was evaluated and showed promising results from the 4-phenyl-5-(4'-nitro-styryl)-1,3,4-thiadiazolium-2-phenylamine chloride derivative.

Este trabalho descreve o efeito inibitório de rubrofusarina (5,6-diidroxi-8-metoxi-2-metilbenzo[g]cromen-4-ona, 1) sobre a enzima DNA topoisomerase II-α humana. Rubrofusarina mostrou total inibição da enzima topisomerase II-α na concentração de 120 µM. Este resultado é semelhante ao observado com etoposida, utilizada como controle positivo. Para a realização deste teste, rubrofusarina foi isolada de Senna macranthera var. nervosa (Voguel) Irwin & Barnebyem e caracterizada por métodos espectroscópicos, incluindo RMN 2D, do produto natural bem como de seu derivado monoacetilado.

This work describes the inhibitory effect of rubrofusarin (5,6-dihydroxy-8-methoxy-2-methylbenzo[g]cromen-4-one, 1) against human DNA topoisomerase II-α. The results for relaxation assays showed total inhibition of topisomerase II-α by rubrofusarin at 120 µM. This result is comparable to the one observed with etoposide as positive control. For this study, rubrofusarin was isolated from Senna macranthera var. nervosa (Voguel) Irwin & Barnebyem and characterized by spectral data, including 2D NMR, as well as its acetylated derivative.

O diterpeno clerodano trans-desidrocrotonina (1), constituinte majoritário de Croton cajucara, tem sua ocorrência correlacionada com o uso dessa planta na medicina popular. Investigações fitoquímicas levaram ao isolamento dos metabólitos 1, cajucarinolida (6), isocajucarinolida (7), trans-crotonina (2), trans-cajucarina B (3), cis-cajucarina B (4), trans-cajucarina A (5), N-metiltirosina, ácido vanílico e ácido 4-hidróxi-benzóico. 6 e 7 foram sintetizados em bons rendimentos através da oxidação de 1 com oxigênio-singlete. Todos os clerodanos foram ensaiados frente a células da leucemia humana K562 e do carcinoma de Ehrlich. Os efeitos inibitórios do crescimento celular foram dependentes da dose para os ensaios com o carcinoma de Ehrlich com IC50 = 166 µM (1), 164 µM (2), 65 µM (6) e 10 µM (7). Além disso, atividade citotóxica moderada foi observada contra as células da leucemia K562 com IC50 = 38 µM (3), 33 µM (5), 36 µM (6) e 43 µM (7). Os 6 e 7 semi-sintéticos mostraram resultados semelhantes quando comparados com os correspondentes clerodanos naturais.

The clerodane-type diterpene, trans-dehydrocrotonin (1) the major component of Croton cajucara has shown striking correlation with its therapeutic use in traditional folk medicine. Phytochemical investigations led to the isolation of the metabolites 1, cajucarinolide (6), isocajucarinolide (7), trans-crotonin (2), trans-cajucarin B (3), cis-cajucarin B (4), trans-cajucarin A (5), N-methyltyrosine, vanillic acid and 4-hydroxy-benzoic acid. 6 and 7 were synthesized in good yield by regiospecific oxidation of 1 using singlet-oxygen. All clerodanes were studied for their cytotoxic effects against human K562 leukemia and Ehrlich carcinoma cells. Ehrlich carcinoma assays with IC50 = 166 µM (1), 164 µM (2), 65 µM (6) and 10 µM (7) related to cell growth inhibitory effects were dose dependent. Furthermore, moderate cytotoxic activity against K562 leukemia cells was observed with IC50 = 38 µM (3), 33 µM (5), 36 µM (6) and 43 µM (7). The semi-synthetic 2, 6 and 7 showed similar results when compared to the corresponding natural clerodanes.

A investigação fitoquímica do extrato metanólico das folhas de Annona dioica (Annonaceae) resultou na identificação dos flavonóides kaempferol (1), 3-O-[3",6"-di-O-p-hidroxicinamoil] -beta-galactopiranosil-kaempferol (2), 6"-O-p-hidroxicinamoil-beta-galactopiranosil-kaempferol (3) e 3-O-beta-galactopiranosil-kaempferol (4). As estruturas foram caracterizadas inequivocamente através de análises espectroscópicas utilizando-se RMN de ¹H e 13C uni e bi-dimensional. Os efeitos citotóxicos dos flavonóides e da fração flavonoídica (FF) foram avaliados frente a células do carcinoma de Ehrlich, utilizando-se o ensaio do MTT (brometo de 3-(4,5-dimetiltiazol-2-il)-2,5-difeniltetrazolium). Os resultados indicaram que 1, 2, 3 e FF apresentam ação anti-proliferativa importante quando comparados com a quercetina. A ação inibitória dos flavonóides sobre as DNA-topoisomerases I e II foi avaliada utilizando-se o ensaio de relaxação sobre o plasmídeo pBR322. Os resultados indicaram ação não seletiva dos flavonóides sobre as DNA-topoisomerases I e II.

Chemical investigation of methanol extract leaves from Annona dioica (Annonaceae) resulted in the identification of flavonoids kaempferol (1), 3-O-[3",6"-di-O-p-hydroxycinnamoyl]-beta-galactopyranosyl-kaempferol (2), 6"-O-p-hydroxycinnamoyl-beta-galactopyranosyl-kaempferol (3) and 3-O-beta-galactopyranosyl-kaempferol (4). The structures were unequivocally characterized by ¹H and 13C NMR spectroscopic analyses using 1D and 2D experiments. The cytotoxic effects of the flavonoids and flavonoid fraction (FF) were evaluated by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay against Ehrlich carcinoma cells. The results indicated that 1, 2, 3 and FF exhibit significant antiproliferative action when compared to quercetin. The inhibitory action on DNA-topoisomerase I and II of all the flavonoids was evaluated by relaxation assays on pBR322 plasmid DNA. The results indicated the inhibitory and non-selective effects of the flavonoids on DNA-topoisomerase I and II.

Novos derivados do lapachol 2, nor-lapachol 3 e da lausona 4 foram sintetizados através do deslocamento nucleofílico das metoxinaftoquinonas 2a, 3a e 4a pela poliamina (PA) N¹-Boc-N5-Bn-espermidina 1a. Os produtos, 2b, 3b e 4b, respectivamente, foram obtidos em bons rendimentos e caracterizados por métodos espectroscópicos e analíticos. Os ensaios preliminares de inibição das enzimas topoisomerases (topo) I e II-alfa mostraram-se promissores: todos os compostos (1a 2b, 3b e 4b) inibiram a atividade catalítica da enzima topo II-alfa na dose de 2 µM. Considerando que somente a PA 1a não inibiu a atividade da enzima na dose de 0,2 µM, as naftoquinonas apresentam-se como fragmentos em potencial para melhorar a atividade de PAs. Nenhum dos compostos inibiu a topo I na dose de 200 µM.

Novel derivatives of lapachol 2, nor-lapachol 3 and lawsone 4 have been synthesized by nucleophilic displacement of the methoxynaphthoquinones 2a, 3a and 4a with the polyamine (PA) N¹-Boc-N5-Bn-spermidine 1a. The respective products 2b-4b were obtained in good yields and characterized by spectroscopic and analytical methods. The inhibitory action of these naphthoquinone-PA conjugates on DNA-topoisomerases (topo) I and II-alpha was evaluated by relaxation assay of supercoiled DNA plasmid. All compounds (1a 2b, 3b and 4b) presented significant inhibition of topo II-alpha catalytic activity at the 2 µM dose. Considering that only PA 1a did not inhibit the enzyme catalytic activity at the 0.2 µM dose, the appended naphthoquinone moiety acts as a "value added" fragment. Compounds 1a 2b, 3b and 4b did not inhibit the enzyme DNA-topo I at the 200 µM dose.

A series of seven Schiff bases have been synthesized from 3,3-diphenylpropilamine and substituted benzaldehydes. These imines were treated with NaBH4 in ethanol affording the corresponding amines in 98-55% yields. A molecular modeling study was performed with the Schiff bases in order to compare the theoretical parameters with the experimental results. The theoretical parameters were obtained by AM1 and PM3 semi-empirical methods. The analysis of charge, electron densities and LUMO coefficients suggested that the most favorable interactions should occur with Schiff bases containing electron-donating groups, in accordance with experimental yields, showing that the higher reactivity is due to higher electrophilic character of imine carbons.