Nitro derivatives and other constituents of Aristolochia melastoma

A phytochemical study of Aristolochia melastoma Manso has led to the isolation and identification of 20 known compounds, including aristolochic acids, sodium aristolochates, lignan, flavonoids, and nitro phenylethyl derivatives. Their structures were established by spectroscopic analysis. The presence of thalictricoside and secoisolariciresinol dimethyl ether diacetate is reported for the first time in the Aristolochiaceae family. In addition, the presence of nitro compounds in this species is significant.

Synthesis of 2-azetidinone derivatives of 6-nitro-1H-indazole and their biological importance

A new series of 3-chloro-1-{[2-(6-nitro-1H-indazol-1-yl)ethyl]amino}-4-(substituted phenyl)-2-azetidinones (4a-j) was synthesized in four steps from 6-nitro-1H-indazole and characterized by IR, ¹H NMR, 13C NMR, FAB-mass spectrometry and chemical methods. Compounds 4(a-j) were screened in vitro for their antibacterial, antifungal and antitubercular activities against some selected microorganism and for their antiinflammatory activity (in vivo) against albino rats (either sex). All above activities of compounds 4(a-j) showed acceptable results.

Isolation and quantitative HPLC-PDA analysis of lupeol in phytopharmaceutical intermediate products from Vernonanthura ferruginea (Less.) H. Rob.

Prior to obtain a standardized dried extract from V. ferruginea, lupeol was first time isolated from leaves and used as chemical maker. An analytical method using HPLC-PDA for lupeol determination in V. ferruginea intermediate products was developed using a C8 reverse-phase column, acetonitrile-acetic acid (99.99:0.01, v/v) as mobile phase at 0.8 mL min-1, oven temperature at 23-25 ºC, sample injection volume at 30 µL and detection at 210 nm. The method presented linearity from 10 to 160 µg mL-1, accuracy, precision, robustness and suitable sensitivity proving to be a useful tool to the obtainment process of lupeol standardized dried extracts of V. ferruginea.

Antiparasitic bromotyrosine derivatives from the Caribbean marine sponge Aiolochroia crassa

Six bromotyrosine-derived compounds were isolated from the Caribbean marine sponge Aiolochroia crassa: 3-bromo-5-hydroxy-O-methyltyrosine (1), 3-bromo-N,N,N-trimethyltyrosinium (2), 3-bromo-N,N,N,O-tetramethyltyrosinium (3), 3,5-dibromo-N,N,N-trimethyltyrosinium (4), 3,5-dibromo-N,N,N,O-tetramethyltyrosinium (5), and aeroplysinin-1 (6). Structural determination was performed using NMR, MS and comparison with literature data. All isolated compounds were screened for their in vitro activity against Leishmania panamensis, Plasmodium falciparum and Trypanosoma cruzi. Compound 4 showed selective antiparasitic activity against Leishmania and Plasmodium parasites. This is the first report of compounds 1, 4 and 5 in the sponge A. crassa and the first biological activity reports for compounds 2-4. This work shows that bromotyrosines are potential antiparasitic agents.

Isolamento e avaliação do potencial citotóxico de derivados fenólicos de Schinus terebinthifolius Raddi (Anacardiaceae)

The EtOH extract from leaves of S. terebinthifolius was subjected to partition between EtOH:H2O and hexane, CH2Cl2, and EtOAc. The phases obtained were evaluated in vitro against human tumoral cell lines and the EtOAc phase exhibited activity. Chromatographic procedures afforded gallic acid (1), methyl (2) and ethyl (3) gallates, trans-catechin (4), quercitrin (5), and afzelin (6), being the first occurrence of 1, 4 and 6 in S. terebinthifolius.In vitro cytotoxic evaluation of 1 - 6 indicated that gallic acid (1) displayed higher activity than ethyl gallate (3) against HL-60 and HeLa cells, while compounds 2, 4 - 6 were inactive.

Carboidratos como fonte de compostos para a indústria de química fina

Coal, oil, natural gas, and shale gas are biomass that is formed millions of years ago. These are non-renewable and depleting, even considering the recent discovery of new sources of oil in the presalt and new technologies for the exploitation of shale deposits. Currently, these raw materials are used as a source of energy production and are also important for the production of fine chemicals. Since these materials are finite and their (oil) price is increasing, it is clear that there will be a progressive increase in the chemical industry to use renewable raw materials as a source of energy, an inevitable necessity for humanity. The major challenge for the society in the twenty first century is to unite governments, universities, research centers, and corporations to jointly act in all areas of science with one goal of finding a solution to global problems, such as conversion of biomass into compounds for the fine chemical industry.Non-renewable raw materials are used in the preparation of fuels, chemical intermediates, and derivatives for the fine chemical industry. However, their stock in nature has a finite duration, and their price is high and will likely increase with their depletion. In this scenario, the alternative is to use renewable biomass as a replacement for petrochemicals in the production of fine chemicals. As the production of biomass-based carbohydrates is the most abundant in nature, it is judicious to develop technologies for the generation of chain products (fuels, chemical intermediates, and derivatives for the fine chemicals industry) using this raw material. This paper presents some aspects and opportunities in the area of carbohydrate chemistry toward the generation of compounds for the fine chemical industry.

Dft theoretical study of energetic nitrogen-rich C4N6H8-n(NO2)n derivatives

Density functional theory (DFT) calculations at the B3LYP/6-31G** theoretical level were performed for a series of guanidine-fused bicyclic skeleton derivatives C4N6H8-n(NO2)n (n = 1 - 6). The heats of formation (HOFs) were calculated by isodesmic reactions, and the detonation properties were evaluated using the Kamlet - Jacobs equations. The bond dissociation energies were also analyzed to investigate the thermal stability and sensitivity of the compounds. The results show that all of the derivatives have high positive HOFs, compound G has the highest theoretical density, and compound F1 has the highest detonation velocity and detonation pressure. Considering both the detonation properties and thermal stabilities, compounds D1 and D4 (3 nitro substituents), E1 - E6 (4 nitro substituents), and G (6 nitro substituents) can be regarded as potential candidates for high-energy density materials.

Phenolic composition and antioxidant properties of Brazilian honeys

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.

DFT study on low molecular weight α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene and α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene S-oxide bridged derivatives

The equilibrium geometries of α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene (DBDT) and α,α-ditert-butyl-4H-cyclopenta[2,1-b,3;4-b']dithiophene S-oxide (DBDTO) were studied at the DFT level of theory with a standard 6-311G* basis set. The molecular structures of the DBDT series were more planar than the corresponding DBDTO series, as revealed by dihedral angles. The UV-visible absorption calculated at TD-DFT/6-311G* showed two absorption peaks for all the molecules except C=S and C=O bridged molecules. In DBDTOs, C=S and C=O bridged molecules showed three and four absorption peaks, respectively. The DBDTOs had lower band gaps and longer wavelengths compared to the corresponding DBDTs.

CHEMICAL STUDY OF Hortia superba (Rutaceae) AND INVESTIGATION OF THE ANTIMYCOBACTERIAL ACTIVITY OF CRUDE EXTRACTS AND CONSTITUENTS ISOLATED FROM Hortia SPECIES

In this paper, the chemical study of Hortia superba and antimycobacterial potential of Hortia species were investigated. Crude extracts and limonoids, alkaloids, dihydrocinnamic acid derivatives and coumarins isolated from Hortia superba, Hortia oreadica and Hortia brasiliana were evaluated against Mycobacterium tuberculosis H37Rv, Mycobacterium kansasii and Mycobacterium avium. The results obtained demonstrated an inhibitory effect of the dichloromethane extract of leaves of H. oreadica (MIC 31.25 µg mL-1), indolequinazoline (15.62 µg mL-1) and furoquinoline (31.25 µg mL-1) alkaloids, and dihydrocinnamic acid derivatives (62.50 µg mL-1), on the growth of M. tuberculosis. These results are promising in relation to the search for biologically active natural products and could be useful in the development of effective new drugs against mycobacteria.

PYROLIGNEOUS LIQUOR PRODUCED FROM ACACIA MEARNSII DE WILD WOOD UNDER CONTROLLED CONDITIONS AS A RENEWABLE SOURCE OF CHEMICALS

Acacia mearnsii de Wild (black wattle) is one of the most important trees planted in Southern Brazil for tannin extraction and charcoal production. The pyrolysis of the black wattle wood used for obtaining charcoal is performed in brick ovens, with the gas fraction being sent directly into the environment. The present study examines the condensable compounds present in the liquor produced from black wattle wood at different thermal degradation conditions, using gas chromatography coupled with mass spectrometry (GC/MS). Branches of black wattle were thermally degraded at controlled ambient and temperature conditions. Overall, a higher variety of compounds were obtained under atmospheric air pressure than under synthetic air pressure. Most of the tentatively identified compounds, such as carboxylic acids, phenols, aldehydes, and low molecular mass lignin fragments, such as guayacol, syringol, and eugenol, were products of lignin thermoconversion. Substituted aromatic compounds, such as vanillin, ethyl vanillin, and 2-methoxy-4-propeny-phenol, were also identified. At temperatures above 200 ºC, furan, 2-acetylfuran, methyl-2-furoate, and furfural, amongst others, were identified as polysaccharide derivatives from cellulose and hemicellulose depolymerization. This study evidences the need for adequate management of the condensable by-products of charcoal production, both for economic reasons and for controlling their potential environmental impact.

SYNTHESIS AND BIOLOGICAL EVALUATION OF SPIRO[INDOLINE-3,4’-PYRANO[2,3-C:6,5-C’]DIPYRAZOL]- 2-ONES IN THE PRESENCE OF SBA-Pr-SO3H AS A NANOCATALYST

Sulfonic acid functionalized SBA-15 nanoporous material (SBA-Pr-SO3H) with a large pore size of 6 nm, a high surface area, high selectivity, and excellent chemical and thermal stability was applied as an efficient heterogeneous nanoporous acid catalyst in the reaction of isatin with pyrazolones under mild reaction conditions. A novel class of symmetrical spiro[indoline-3,4'-pyrano[2,3-c:6,5-c']dipyrazol]-2-one derivatives was successfully obtained in high yields. Comparison of these results with those reported in the literature shows that the current method is efficient, and results in better reaction times and yields of the desired products. Other advantages of this new method are its operational simplicity, easy work-up procedure, and the use of SBA-Pr-SO3H as a reusable and environmentally benign nanoreactor, such that the reaction proceeds easily in its nanopores. We also tested the antimicrobial activity of the prepared compounds using the disc diffusion method, and some of the synthesized compounds exhibited the best results against B. subtilis and S. aureus.

UM MÉTODO EFICIENTE PARA A OBTENÇÃO DE DERIVADOS DE 1-ALQUILAMINO-2,4-DINITROBENZENO E A REDUÇÃO REGIOSSELETIVA PARA A OBTENÇÃO DE DERIVADOS DE 1-ALQUILAMINO-2-AMINO-4-NITROBENZENO

Both primary and secondary amines react with 2,4-dinitrochlorobenzene to give derivatives of 1-alkylamino-2,4-dinitrobenzene. These compounds are important intermediates for the synthesis of a diverse range of products. The methodology reported in the present study involves either the room temperature reaction or heating at 70 °C in ethanol in the presence of triethylamine. This transformation occurs via a nucleophilic substitution reaction. The 1-alkylamino-2,4-dinitrobenzene derivatives were obtained in greater than 90% purified yield. The selective reduction of dinitro compounds is an important synthetic strategy for the synthesis of intermediates for dyes, pharmaceuticals and agrochemicals. The use of SnCl2 as a suspension in EtOAc is a promising method for the regio- and chemo-selective reduction of 1-alkylamino-2,4-dinitrobenzenes to 1-alkylamino-2-amino-4-nitrobenzenes. These products are useful intermediates in organic synthesis.

SÍNTESE DE DERIVADOS DE FENANTRIDINONAS POR ARILAÇÃO DIRETA. CARACTERIZAÇÃO DOS ESPECTROS DE ABSORÇÃO E EMISSÃO DE EXEMPLOS REPRESENTATIVOS

The phenanthridinone heterocyclic system has attracted considerable attention in recent years due to the diverse array of physical, chemical and pharmacological properties demonstrated by natural and synthetic derivatives. As a consequence there has been considerable development of synthetic methodology for the synthesis of this and related heterocyclic ring systems. The synthetic literature is discussed and is compared with a direct arylation methodology for the intramolecular cyclization of tertiary (2-iodo)benzoylamides to generate the biaryl bond of these compounds. The efficient methodology allowed the synthesis of a number of previously unknown phenanthridinone products. The photoluminescent properties of representative examples were characterized and it is proposed that the previously unknown compound 1s reveals dual fluorescence in a manner similar to the known compound 1r.

Immunolocalisation of secreted-excreted products of Meloidogyne spp. using polyclonal and monoclonal antibodies

Molecules expressed at the surface cuticle (SC) of plant parasitic nematodes represent the primary plant-nematode interface, and together with secreted-excreted (S-E) products are probably the first signals perceived by the host. These molecules, which are released into plant tissue, probably play important roles in the host-parasite interactions. Characterisation of these antigens will help in the identification of nematode targets useful for novel control strategies, which interfere with the nematode infection of plants. Three monoclonal (MAbs) and three polyclonal (PAbs) antibodies produced to S-E products of Meloidogyne spp. and Heterodera avenae were used to examine their reactivity towards M. incognita and/or M. arenaria second stage juveniles and adult females. The three PAbs showed cross-reactivity with M. incognita and M. arenaria. Antibody Roth-PC 373 strongly recognised molecules present in the SC, amphids and intestine, antibody Roth-PC 389 recognised the nematode amphids and metacorpus, while antibody Roth-PC 419 bound to molecules present in the subventral glands. Reactivity of the MAbs was only tested against M. arenaria. Monoclonal antibody Roth-MAb T116C1.1 showed intense reactivity with molecules present in the amphidial and phasmidial glands. Monoclonal antibodies Roth-MAb T46.2 and T42D.2 labeled the nematode amphids and molecules present in the nematode oesophagus (metacorpus), respectively.