Phenolic Derivatives from Fruits of Dipteryx lacunifera DUCKE and Evaluation of Their Antiradical Activities

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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.

Comparative investigation of the cleavage step in the synthesis of model peptide resins: Implications for N-alpha-9-fluorenylmethyloxycarbonyl-solid phase peptide synthesis

Based on our studies of the stability of model peptide-resin linkage in acid media, we previously proposed a rule for resin selection and a final cleavage protocol applicable to the N-alpha-tert-butyloxycarbonyl (Boc)-peptide synthesis strategy. We found that incorrect choices resulted in decreases in the final synthesis yield, which is highly dependent on the peptide sequence, of as high as 30%. The present paper continues along this line of research but examines the N-alpha-9-fluorenylmethyloxycarbonyl (Fmoc)-synthesis strategy. The vasoactive peptide angiotensin II (All, DRVYIHPF) and its [Gly(8)]-All analogue were selected as model peptide resins. Variations in parameters such as the type of spacer group (linker) between the peptide backbone and the resin, as well as in the final acid cleavage protocol, were evaluated. The same methodology employed for the Boc strategy was used in order to establish rules for selection of the most appropriate linker-resin conjugate or of the peptide cleavage method, depending on the sequence to be assembled. The results obtained after treatment with four cleavage solutions and with four types of linker groups indicate that, irrespective of the circumstance, it is not possible to achieve complete removal of the peptide chains from the resin. Moreover, the Phe-attaching peptide at the C-terminal yielded far less cleavage (50-60%.) than that observed with the Gly-bearing sequences at the same position (70-90%). Lastly, the fastest cleavage occurred with reagent K acid treatment and when the peptide was attached to the Wang resin.

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.

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.

Direct electron paramagnetic resonance monitoring of the peptide synthesis coupling reaction in polymeric support

This work demonstrates, for the first time. a time-resolved electron paramagnetic resonance (EPR) monitoring of a chemical reaction occurring in a polymeric structure. The progress of the coupling of a N-alpha-tert-butyloxycarbonyl-2.2.6.6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid (Boc-TOAC) spin probe to a model peptide-resin was followed through EPR spectra. Progressive line broadening of EPR peaks was observed, indicative of an increased population of immobilized spin probe molecules attached to the solid support. The time for spectral stabilization of this process coincided with that determined in a previous Coupling study. thereby validating this in situ quantitative monitoring of the reaction. In addition, the influence of polymer swelling degree and solvent viscosity, as well as of the steric hindrance within beads. on the rate of coupling reaction was also addressed. A deeper evaluation of the latter effect was possible by determining unusual polymer parameters such as the average site-site distance and site-concentration within resin beads in each solvent system. (c) 2006 Elsevier Ltd. All rights reserved.

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%).

Influence of the cultivation system in the aroma of the volatile compounds and total antioxidant activity of passion fruit

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Correlation between structural data and spectroscopic studies of a new beta-diketonate complex with trivalent europium and gadolinium

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)