Antibacterial activity of labdane diterpenoids from Stemodia foliosa

As part of a continuing interest in exploring the chemistry of Brazilian medicinal plants, three new labdane diterpenoids, 6 alpha-acetoxymanoyl oxide (1), 6 alpha-malonyloxymanoyl oxide (2), and 6 alpha-malonyloxy-n-butyl ester manoyl oxide (3), together with the known betulinic acid, lupeol, sitosterol, and stigmasterol, were isolated from the aerial parts of Stemodia foliosa. The structures of 1-3 were established on the basis of interpretation of spectroscopic data, including HRESIMS, and 1D and 2D NMR techniques. All compounds were tested against a bacteria panel consisting of Staphylococcus aureus, Bacillus cereus, B. subtilis, B. anthracis, Micrococcus luteus, Mycobacterium smegmatis, and M. phlei. Compound 2 showed, moderate activity against these strains, with MIC values in the range 7-20 mu g/mL.

Catálise estereoespecífica de estireno por titanocenos alquil-substituídos do tipo (RCp)2TiCl2

Uma série de sete complexos alquil substituídos do tipo (RCp)2TiCl2 (R= H, etila, n-propila, iso-propila, n-butila, iso-amila, ciclo-hexila) foi preparada juntamente com o ainda inédito contendo R= sec-butila, e o efeito do substituinte na polimerização do estireno foi investigada à temperaturas de polimerização de 0 e 50 ºC. Foi encontrado que R = n-butila maximiza a produção de poliestireno sindiotático. Ligantes alquilas com R = RCH2- são superiores aos R = RR CH- e ao precursor Cp2TiCl2 na produção de poliestireno sindiotático de alto peso molecular.

MISTURAS DE HERBICIDAS: EFEITOS DE ADJUVANTES NO CONTROLE DE PLANTAS INFESTANTES NA CULTURA da SOJA

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Formação de cobertura vegetal e manejo de plantas daninhas na cultura da soja em sistema plantio direto

Objetivou-se com este trabalho avaliar a formação de cobertura vegetal por Brachiaria brizantha e B. decumbens, bem como as interações entre as coberturas vegetais, as dosagens do herbicida glifosato e a aplicação da mistura fluazifop-p-butil + fomesafen, no manejo das plantas daninhas e na produção da soja MG/BR 46 - Conquista em sistema plantio direto. Utilizou-se delineamento experimental de blocos ao acaso, num esquema de parcelas subsubdivididas, com quatro repetições. Testaram-se duas espécies de braquiária (B. brizantha e B. decumbens), duas dosagens do herbicida glifosato (1,44 e 2,16 kg e.a. ha-1) e duas dosagens da mistura fluazifop-p-butil + fomesafen (0 e 0,25 + 0,25 kg i.a. ha-1). Foram realizadas avaliações de matéria seca das coberturas, eficácia do glifosato, rebrote das coberturas, altura das plantas de soja, número de vagens, altura de inserção da primeira vagem, acamamento, dificuldade de colheita, massa de 100 grãos e produtividade. Concluiu-se que B. decumbens e B. brizantha proporcionaram adequada cobertura do solo durante todo o ciclo da cultura, que a dosagem de 1,44 kg e.a. ha-1 de glifosato foi suficiente para o controle das duas espécies de braquiária e que a produtividade da cultura da soja não foi alterada significativamente pela palhada das duas espécies estudadas nem pela dosagem do glifosato, enquanto a aplicação de fluazifop-p-butil + fomesafen como controle complementar refletiu em maior produtividade e em menor dificuldade de colheita.

Efeitos estéricos e eletrônicos de substituintes alquilas em catalisadores titanocênicos solúveis na polimerização sindioespecífica de estireno

Titanocenos são catalisadores solúveis conhecidos para a polimerisação estereoespecífica de olefinas pró-quirais como o estireno. Nesse trabalho descrevemos as relações entre as características do poliestireno e a estrutura do precursor do catalisador, de fato aqueles da família (RCp)2TiCl2 (R = H, etila, iso-propila, n-propila, sec-butila, n-butila, iso-amila e ciclohexila). Todos os catalisadores são ativos para a produção de poliestireno acima de zero graus centígrados. A sindiotaticidade dos polímeros são dependentes da cadeia lateral dos anéis aromáticos do titanoceno e da temperatura da polimerização. A relação entre os fatores estéricos e eletrônicos do precursor do catalisador e os produtos de polimerização são apresentados e discutidos.

Rendimento e composição das aguardentes de cana, laranja e uva com utilização de lecitina no processo fermentativo

O presente trabalho foi desenvolvido com o objetivo de avaliar o efeito da adição de lecitina aos mostos de cana, laranja e uva sobre o rendimento e composição das aguardentes. O delineamento empregado para a análise estatística foi o de blocos casualizados, no esquema fatorial 2x3, empregando-se dois fatores - lecitina e mosto - em dois níveis para lecitina: ausência (índice um) e presença (índice dois); e em três níveis para mosto: cana, laranja e uva. A metodologia empregada foi a recomendada pelo setor aguardenteiro e as análises químicas dos componentes secundários foram realizadas por cromatografia gasosa e espectrofotometria. Pelos resultados, conclui-se que quando se adiciona lecitina aos mostos de cana, laranja e uva, o vinho obtido após a fermentação tem maior concentração de glicerol, e as aguardentes produzidas pela destilação têm maior concentração de isobutanol. Já nos mostos em que foi adicionada a lecitina, o rendimento alcoólico total das aguardentes foi menor do que nos mostos que não a recebeu. Os componentes secundários acetaldeído, acetato de etila e acidez total aumentaram com o aumento da acidez nos vinhos. Por outro lado, o propanol, isobutanol e álcool isoamílico aumentaram com os aumentos dos pH e das concentrações nos mostos, dos aminoácidos treonina, valina e leucina. A concentração do furfural foi maior nas aguardentes provenientes dos mostos de cana e laranja.

Dose- and sex-related carcinogenesis by N-bis(2-hydroxypropyl)nitrosamine in Wistar rats

An initiation-promotion medium-term bioassay for detection of chemical carcinogens, developed in the male F344 rat, uses 0.1% N-bis(2-hydroxypropyl)nitrosamine (DHPN) among five genotoxic chemicals for the initiation of carcinogenesis in multiple organs. To establish this bioassay in the Wistar strain, the effects of two dose levels of DHPN were evaluated on the main DHPN rat target organs: lung, thyroid gland, kidneys and liver. Four groups of male and female animals were studied: Control--untreated group; Multi-organ initiated group (also referred to as DMBDD, based on the initials of the five initiators)-treated sequentially with N-diethylnitrosamine (DEN, i.p.), N-methyl-N-nitrosourea (MNU, i.p.), N-butyl-N-(4-hydroxy butyl)nitrosamine (BBN, drinking water), N, N'-dimethylhydrazine (DMH, s.c.) and DHPN (drinking water) for 4 weeks; a third group treated with 0.1% DHPN in drinking water for 2 weeks and the last group treated with 0.2% DHPN in drinking water for 4 weeks. The animals were sacrificed after 30 weeks. DHPN at 0.2% induced preneoplasia in the liver and kidneys of rats of both sexes, the number and area of the putative preneoplastic liver glutathione S-transferase-positive hepatocyte foci being significantly increased in these animals. It also induced benign and malignant tumors in female and in male rats. However, there was no relationship between the increased incidence of preneoplastic lesions and tumor development in the 0.2% DHPN-exposed groups of both sexes. DHPN at 0.1% induced only a few preneoplastic lesions in the liver and kidney and no tumors in both male and female rats. A clear dose and sex-related carcinogenic activity of DHPN was registered, although Wistar rats of both sexes showed a relative resistance to the carcinogenic activity of this compound.

THE CATHODIC CLEAVAGE OF THE NITROBENZENESULFONYL GROUP FROM ALIPHATIC-AMINES IN N,N-DIMETHYLFORMAMIDE

The reduction of benzenesulfonyl derivatives of n-butylamine and N,N-di-n-butylamine with nitro substituents at the 2, 3 and 4 positions of the phenyl ring in N,N-dimethylformamide is reported. The N,N-di-n-butyl-4- and N-n-butyl-2-nitrobenzenesulfonamides are reduced in two cathodic steps. The first one, at about -0.90 V vs. SCE, a reversible one-electron process, gives a stable anion radical. The second reduction step at -1.70 V vs. SCE leads to cleavage of the S-N bond in good yields (> 70%). It is shown that the reduction of the N-n-butyl-3- and N-n-butyl-4-nitrobenzenesulfonamide is different, with three reduction steps. The first reduction step occurs with the formation of an unstable anion radical, which decomposes via N-H bond cleavage. The reduction of this sulfonamide anion occurs at -1.16 V vs. SCE and the third cathodic step arises at -1.70 V vs. SCE when the remaining radical anion is reduced to its dianion. The S-N bond cleavage is rapid but is always a minor process. The mechanisms of the reduction are discussed.

EPR investigation of the influence of side chain protecting groups on peptide-resin solvation of the Asx and Glx model containing peptides

In spite of all progressive efforts aiming to optimize SPPS, serious problems mainly affecting the assembly of aggregating sequences have persisted. Following the study intended to unravel the complex solvation phenomenon of peptide-resin beads, the XING and XAAAA model aggregating segments were labeled with a paramagnetic probe and studied via EPR spectroscopy. Low and high substituted resins were also comparatively used, with the X residue being Asx or Glx containing the main protecting groups used in the SPPS. Notably, the cyclo-hexyl group used for Asp and Glu residues in Boc-chemistry induced greater chain immobilization than its tert-butyl partner-protecting group of the Fmoc strategy. Otherwise, the most impressive peptide chain immobilization occurred when the large trytil group was used for Asn and Gln protection in Fmoc-chemistry. These surprising results thus seem to stress the possibility of the relevant influence of the amino-acid side chain protecting groups in the overall peptide synthesis yield. (C) 2007 Elsevier Ltd. All rights reserved.

Titanium and zirconium complexes containing sterically hindered hydrotris(pyrazolyl)borate ligands: synthesis, structural characterization, and ethylene polymerization studies

The synthesis, characterization and ethylene polymerization behavior of a set of Tp'MCl3 complexes (4, M = Ti, Tp' HB(3-neopentyl-pyrazolyl)(3)(-) (Tp(NP)); 5, M = Ti, Tp'= HB(3-tert-butyl-pyrazolyl)(3)(-) (Tp(tBu)); 6, M = Ti, Tp' = HB(3-phenyl-pyrazolyl)(3)(-) (Tp(Ph)); 7, M = Zr, Tp' = HB(3-phenyl-pyrazolyl)(3)(-) (Tp(ph)); 8, M = Zr, Tp' = HB(3-tert-butyl-pyrazolyl)(3)(-) (Tp(tBu))) is described. Treatment of these tris(pyrazolyl)borate Group IV compounds with methylalumoxane (MAO) generates active catalysts for ethylene polymerization. For the polymerization reactions performed in toluene at 60 degreesC and 3 atm of ethylene pressure, the activities varied between 1.3 and 5.1 X 10(3) g of PE/mol[M](.)h. The highest activity is reached using more sterically open catalyst precursor 4. The viscosity-average molecular weights ((M-v) over bar) of the PE's produced with these catalyst precursors varying from 3.57 to 20.23 x 10(5) gmol(-1) with melting temperatures in the range of 127-134 degreesC. Further polymerization studies employing 7 varying Al/Zr molar ratio and temperature of polymerization showed that the activity as well as the polymer properties are dependent on these parameters. In that case, higher activity was attained at 60 degreesC. The viscosity-average molecular weights of the polyethylene's decreases with increasing AI/Zr molar ratio. (C) 2003 Elsevier B.V. All rights reserved.

Surface-enhanced resonance Raman scattering as an analytical tool for single molecule detection

A perylene derivative, n-(n-butyl)-n'-(4-aminobutyl) perylene-3,4,9,10-tetracarboxylic acid diimide (simplified as nBu-PTCD-(CH2)(4)-NH2) has been chosen as the target molecule for studies involving single molecule detection (SMD) using Raman scattering. The enhancement of the Raman signal is the result of the multiplicative effects of two phenomena, resonance Raman scattering (RRS) and surface-enhanced Raman scattering (SERS), which leads to the resulting surface-enhanced resonance Raman scattering (SERRS) process. The SERRS spectra from a single molecule have been collected using both silver and gold colloids. The SMD detection of the fundamental vibrational frequencies characteristic of nBu-PTCD-(CH2)(4)-NH2 is complemented with the detection of some overtones and combinations from ring stretching modes at the single molecule level. The background characterization of the ensemble vibrational spectroscopy of the target perylene and its SERRS is also presented, which includes the UV-vis absorption, experimental and calculated Raman scattering and infrared absorption, and molecular organization using reflection-absorption infrared spectroscopy (RAIRS).

Electroluminescence of a device based on europium beta-diketonate with phosphine oxide complex

Rare earth (RE) ions have spectroscopic characteristics to emit light in narrow lines, which makes RE complexes with organic ligands candidates for full color OLED (Organic Light Emitting Diode) applications. In particular, beta-diketone rare earth (RE(3+)) complexes show high fluorescence emission efficiency due to the high absorption coefficient of the beta-diketone and energy transfer to the central ion. In this work, the fabrication and the electroluminescent properties of devices containing a double and triple-layer OLED using a new beta-diketone complex, [Eu(bmdm)(3)(tppo)(2)], as transporting and emitting layers are compared and discussed. The double and triple-layer devices based on this complex present the following configurations respectively: device 1: ITO/TPD (40 nm)/[Eu(bmdm)(3)(tppo)(2)] (40 nm)/Al (150 nm); device 2: ITO/TPD (40 nm)/[Eu(bmdm)(3) (tppo)(2)] (40 nm)/Alq(3) (20 nm)/Al (150 nm) and device 3: ITO/TPD (40 nm)/bmdm-ligand (40 nm)/Al (150 nm), were TPD is (N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1-biphenil-4,4-diamine) and bmdm is butyl methoxy-dibenzoyl-methane. All the films were deposited by thermal evaporation carried out in a high vacuum system. These devices exhibit high intensity photo- (PL) and electro-luminescent (EL) emission. Electroluminescence spectra show emission from Eu(3+) ions attributed to the (5)D(0) to (7)F(J) (J = 0, 1, 2, 3 and 4) transitions with the hypersensitive (5)D(o) -> (7)F(2) transition (around 612 nm) as the most prominent one. Moreover, a transition from (5)D(1) to (7)F(1) is also observed around 538 nm. The OLED light emission was almost linear with the current density. The EL CIE chromaticity coordinates (X = 0.66 and Y = 0.33) show the dominant wavelength, lambda(d) = 609 nm, and the color gamut achieved by this device is 0.99 in the CIE color space. (c) 2006 Elsevier B.V. All rights reserved.

A new beta-diketone complex with high color purity

In this work a new europium (III) complex with the following formula NH(4) [Eu(bmdm)(4)] was synthesized and characterized. The bmdm (butyl methoxy-dibenzoyl-methane) is a P-diketone molecule used as UV radiation absorber in sunscreen formulations. Coordination of this ligand to the Eu(3+) ion was confinned by FT-IR, while the Raman spectrum suggests the presence of NH(4)(+) ions. The photoluminescence spectra present narrow lines arising from f-f intra-configurational transitions (5)D(0-)(7)F(0,1,2,3,4), dominated by the hypersensitive (5)D(0)-(7)F(2) transition. In the spectrum recorded at 77 K, all transitions split into 2J + 1 lines suggesting that there is just one symmetry site around Eu(3+) ion. This symmetry is not centrosymmetric. The calculated intensity parameters are ohm(2) = 30.5 x 10(-20) cm(2) and ohm(4) = 5.91 x 10(-20) cm(2) for this complex. The CIE chromaticity coordinates (x = 0.67 and y = 0.32) show a dominant wavelength of 615 nm. The color gamut achieved by this complex is a 100% in the CIE color space. (c) 2005 Elsevier B.V. All rights reserved.

Decreased Total Antioxidant Capacity in Plasma, but Not Tissue, in Experimental Colitis

The aim of the present work was to compare colonic mucosa and plasmatic oxidative stress measured concomitantly and with different degrees of injury in rats with colitis induced by trinitrobenzene sulfonic acid. Three groups were studied: control group, colitis group, and colitis exacerbated by diclofenac. Enzymatic markers of colon injury showed enhanced activity in both groups with colitis. The colitis group treated with diclofenac presented higher colonic damage score than the other groups. In both groups with colitis, higher values of tert butyl hydroperoxide-initiated-chemiluminescence and thiobarbituric acid-reactive substances in tissue and decreased total radical-trapping antioxidant potential (TRAP) levels in plasma were found. In conclusion, independently of the degree of colonic mucosa injury and inflammation, oxidative stress in tissue occurs as a consequence of pro-oxidants increase, and is not explained by a reduction of antioxidant defenses. In both conditions, TRAP determination decreases in plasma, but not in tissue.

Seletividade e eficácia de herbicidas inibidores da enzima accase na cultura da mamona

This experiment aimed to evaluate the selectivity and efficacy of ACCase-inhibiting herbicides in castor bean crop, at Paraguacu Paulista, São Paulo, during the 2002/03 agricultural season. The experimental design used was randomized complete blocks, with eleven treatments and four replicates, constituted by the following herbicides and adjuvants: fluazifop-p-butyl 313 g ha(-1)) + Agral (TM) 0.2% v/v); sethoxydim 322 g ha(-1)) + Assist (TM) 0.5% v/v); haloxyfop-methyl 120 g ha(-1)) + Assist (TM) 0.5% v/v); clethodim+ fenoxaprop-p-ethyl 75 g ha(-1)) + Assist (TM) 0.5% v/v); quizalofop-pethyl 125 g ha(-1)) + Assist (TM) 0.5% v/v); clethodim 156 g ha(-1)) + Assist (TM) 0.5% v/v); propaquizafop 175 g ha(-1)) + Assist (TM) 0.5% v/v); tepraloxydim 400 g ha(-1)) + Dash (TM) 0.5% v/v); butroxydim 100 g ha(-1)) + Dash (TM) 0.5% v/v); isoxaflutole 60 g ha(-1)) and weed-free check. At the moment of application, castor bean plants presented 4 to 6 leaves and Cenchrus echinatus, 1 to 5 tillers. AL Guarany 2002 cultivar presented high selectivity to ACCase-inhibiting herbicides, without visible symptoms of phytotoxicity in 14 DAA days after application), except for tepraloxydim, whose symptoms persisted until 21 DAA, and isoxaflutole HPPD inhibiting), which showed injuries in older leaves and significant yield reduction. C. echinatus infestation was efficiently controlled by ACCase-inhibiting herbicides between 14 and 21 DAA (>= 95.0%).