Spectroscopic and theoretical studies of some N-methoxy-N-methyl-2-[(4 `-substituted) phenylsulfonyl]propanamides

The analysis of the IR carbonyl band of the N-methoxy-N-methyl-2-[(4`-substituted)phenyisulfonyI]propanamides Y-PhSO(2)CH(Me)C(O)N(OMe)Me (Y = OMe 1, Me 2, H 3, Cl 4, NO(2) 5), supported by HF/6-31G(d,p) calculations of 3,, indicated the existence of two gauche conformers (g(1) and g(2)), the g, conformer being the most stable and the least polar one (in gas phase and in solution). Both conformers are present in solution of the non polar solvent (CCl(4)) for 1-5 and in solution of the more polar solvents (CHCl(3)) for 1. 4, 5 and (CH(2)Cl(2)) for 5, while only the g(1) conformer is present in solution of the most polar solvent (CH(3)CN) for 1-5. The g, and g2 conformers correspond to the enantiomeric pairs of diastereomers (diast(1) and diast(2)) whose relative configurations are [C(3)(R)N(R)]/[C(3)(s)N(s)] and [C(3)(R)N(s)]/[C(3)(s)N(R)], respectively. The computed carbonyl frequencies for g(1) (diast(1)) and g(2) (diast(2)) stereoisomers of3 match well the experimental values. The NBO analysis, for 3 shows the important role of the orbital interactions in conformer stabilization and the overall balance of these interactions corroborates that the g, conformer is more stable than the 92 one. The observed abnormal solvent effect on the relative intensities of the carbonyl doublet components is attributed to the molecular crowding in the g2 conformer which hinders its solvation in comparison to the g, conformer (diast(1)). X-ray single crystal analysis performed for 3 shows the existence Of two 92, and g(1b) conformers of diastereomers (diast2, and diast(1b)) whose absolute configurations are [C(3)(R)N(s)] and [C(3)(R)N(R)], respectively. The larger population and. thus, the larger stabilization of the g(2), conformer over the gib form in the crystals may be associated with a larger energy gain deriving from dipole moment coupling in the former conformer along with a series of C-H center dot center dot center dot O electrostatic and hydrogen bond interactions, (C) 2009 Elsevier B.V. All rights reserved.

Spectroscopic and theoretical studies of some N-methoxy-N-methyl-2-[(4 `-substituted) phenylthio]propanamides

The analysis of the IR carbonyl band of the N-methoxy-N-methyl-2-[(4`-substituted)phenylthio]propanamides Y-PhSCH(Me)C(O)N(OMe)Me (Y=OMe 1, Me 2, H 3, Cl 4, NO(2) 5), supported by B3LYP/cc-pVDZ calculations of 3, indicated the existence of two gauche conformers (g(1) and g(2)), the g(1) conformer being the more stable and the less polar one (in gas phase and in solution). Both conformers are present in solution of the polar solvents (CH(2)Cl(2) and CH(3)CN) for 1-5 and in solution of the less polar solvent (CHCl(3)) for 1-4, while only the g(1) conformer is present in solution of non polar solvents (n-C(6)H(14) and CCl(4)) and in solution of CHCl(3) for 5. NBO analysis shows that both the sigma(C-S) -> pi*(C=O) (hyperconjugative) and the pi(C=O) -> sigma*(C-S) orbital interactions contribute almost to the same extent for the stabilization of g(1) and g(2) conformers. The pi*(C=O) -> sigma*(C-S), n(S) -> pi*(C=O) and the n(S) -> pi*(C=O) orbital interactions stabilize more the g(1) conformer than the g(2) one. Moreover, the suitable geometry of the g(1) conformer leads to its stabilization through the LP(O2) -> sigma*(C8-H11) orbital interaction (hydrogen bond) along with the strong O([CO])(delta-) center dot center dot center dot H([O-Ph])(delta+) electrostatic interaction. On the other hand, the appropriate geometry of the g(2) conformer leads to its stabilization by the LP(O22) -> sigma*(C9-H13) orbital interaction (hydrogen bond) along with the weak O([OMe])(delta-) center dot center dot center dot H([o`-Ph])(delta+) electrostatic static interaction. As for the 4`-nitro derivative 5 the ortho-phenyl hydrogen atom becomes more acidic, leading to a stronger O([CO])(delta-) center dot center dot center dot H([o-Ph])(delta+) interaction and, thus, into a larger stabilization of the g(1) conformer in the whole series. This trend is responsible for the unique IR carbonyl band in CHCl(3) solution of 5. The larger occupancy of the pi*(C=O) orbital of the g(1) conformer relative to that of the g(2) conformer, along with the O([CO])(delta-) center dot center dot center dot H([o-Ph])(delta+) electrostatic interaction (hydrogen bond) justifies the lower carbonyl frequency of the g(1) conformer with respect to the g(2) one, in gas phase and in solution. (C) 2008 Elsevier B.V. All rights reserved.

Square wave adsorptive cathodic stripping voltarnmetry automated by sequential injection analysis - Potentialities and limitations exemplified by the determination of methyl parathion in water samples

This paper describes the development and evaluation of a sequential injection method to automate the determination of methyl parathion by square wave adsorptive cathodic stripping voltammetry exploiting the concept of monosegmented flow analysis to perform in-line sample conditioning and standard addition. Accumulation and stripping steps are made in the sample medium conditioned with 40 mmol L-1 Britton-Robinson buffer (pH 10) in 0.25 mol L-1 NaNO3. The homogenized mixture is injected at a flow rate of 10 mu Ls(-1) toward the flow cell, which is adapted to the capillary of a hanging drop mercury electrode. After a suitable deposition time, the flow is stopped and the potential is scanned from -0.3 to -1.0 V versus Ag/AgCl at frequency of 250 Hz and pulse height of 25 mV The linear dynamic range is observed for methyl parathion concentrations between 0.010 and 0.50 mgL(-1), with detection and quantification limits of 2 and 7 mu gL(-1), respectively. The sampling throughput is 25 h(-1) if the in line standard addition and sample conditioning protocols are followed, but this frequency can be increased up to 61 h(-1) if the sample is conditioned off-line and quantified using an external calibration curve. The method was applied for determination of methyl parathion in spiked water samples and the accuracy was evaluated either by comparison to high performance liquid chromatography with UV detection, or by the recovery percentages. Although no evidences of statistically significant differences were observed between the expected and obtained concentrations, because of the susceptibility of the method to interference by other pesticides (e.g., parathion, dichlorvos) and natural organic matter (e.g., fulvic and humic acids), isolation of the analyte may be required when more complex sample matrices are encountered. (C) 2007 Elsevier B.V. All rights reserved.

Stereochemical and electronic interaction studies of some N-methoxy-N-methyl-2-[(4 `-substituted)phenylsulfinyl]propanamides

The (1)H NMR spectra of N-methoxy-N-methyl-2-[(4`-substituted)phenylsulfinyl]-propanamides [Y-Ph-S(O)CH(Me)C(O)N(OMe)Me; Y = OMe 1, Me 2, H 3. Cl 4, NO(2) 5] along with the X-ray diffraction analysis of the nitro-derivative (5). have shown the existence of two pairs of diastereomers (racemic mixture) [C(R)S(S)/C(S)S(R) (diast(1)) and C(R)S(R)/C(S)S(S) (diast(2))] in the ratio of ca. 7:3. respectively. The v(CO) IR analysis of the title compounds supported by HF and B3LYP/6-31G** calculations of 3 and of the parent N-methoxy-N-methyl-propanamide (6) by HF, have shown that diast(1) exists in an equilibrium between the two more polar and more stable quasi-cis (q-c(1) and q-c(2)) conformers and the gauche(g) conformer. The population of the g conformer in the equilibrium increases with the increase in the solvent polarity, which is attributed to a larger solvation effect on the carbonyl and sulfinyl groups. Diast(2) of compound 3 occurs in the gas phase as an equilibrium between the most stable quasi-gauche (q-g) conformer and the quasi-cis (q-c) conformer, both presenting very similar dipole moments. The former is stabilized by electrostatic and charge transfer interactions, which results in a less solvated spatial arrangement. Moreover, all conformers of both diastereomers are stabilized by several intramolecular hydrogen bonds. X-ray single crystal analysis performed for diast(1) and for diast(2) of 5 indicates that both stereoisomers assume, in the solid state, the anti-clinal (gauche) conformation. For the crystal packing, diast(1) of 5 is made up of three molecules joined through two centro-symmetric H center dot center dot center dot O hydrogen bonds. (C) 2008 Elsevier B.V. All rights reserved.

Quantitative ester analysis in cachaca and distilled spirits by gas chromatography-mass spectrometry (GC-MS)

An analytical procedure for the separation and quantification of ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl lactate, ethyl octanoate, ethyl nonanoate, ethyl decanoate, isoamyl octanoate, and ethyl laurate in cachaca, rum, and whisky by direct injection gas chromatography-mass spectrometry was developed. The analytical method is simple, selective, and appropriated for the determination of esters in distilled spirits. The limit of detection ranged from 29 (ethyl hexanoate) to 530 (ethyl acetate) mu g L-1, whereas the standard deviation for repeatability was between 0.774% (ethyl hexanoate) and 5.05% (isoamyl octanoate). Relative standard deviation values for accuracy vary from 90.3 to 98.5% for ethyl butyrate and ethyl acetate, respectively. Ethyl acetate was shown to be the major ester in cachaca (median content of 22.6 mg 100 mL(-1) anhydrous alcohol), followed by ethyl lactate (median content of 8.32 mg 100 mL(-1) anhydrous alcohol). Cachaca produced in copper and hybrid alembic present a higher content of ethyl acetate and ethyl lactate than those produced in a stainless-steel column, whereas cachaca produced by distillation in a stainless-steel column present a higher content of ethyl octanoate, ethyl decanoate, and ethyl laurate. As expected, ethyl acetate is the major ester in whiskey and rum, followed by ethyl lactate for samples of rum. Nevertheless, whiskey samples exhibit ethyl lactate at contents lower or at the same order of magnitude of the fatty esters.

Thioxanthone Sensitized Photodegradation of Poly(alkyl methacrylate) Films

The thioxanthone-sensitized photodegradation of poly(alkyl methacrylate) films [alkyl = methyl, ethyl, butyl, and hexyl] was studied using near UV-vis light. The photooxidation process continued even after the total consumption of the sensitizer, possibly due to the excitation of the ketyl groups formed during the first stages of the process. The rate of oxidation, as well as the formation of hydroxy, peroxy, and ketyl groups was faster for polymers with larger ester groups. The decrease of the molecular weight of the degradated polymers was also larger for the hexyl substituted polymer. The side-chain size effect was attributed to the larger amount of secondary hydrogens available for abstraction by the triplet state of thioxanthone, present in the larger ester groups. The lower glass transition temperature of the hexyl substituted polymer allows a better diffusion of oxygen to the deeper layers of the films that also contributes to the faster photodegradation rate. (C) 2009 Wiley Periodicals, Inc. J Appl Polym Sci 115: 1283-1288, 2010

Selectivity of the plant growth regulators trinexapac-ethyl and sulfometuron-methyl to cultivated species

The aerial spraying of plant ripeners on sugar cane (Saccharum officinarum L.) crops causes often the contamination of neighboring areas, which subsidizes formal complaints from the neighbors. These contaminations are due to spraying taking place during inadequate environmental conditions or from technical mistakes during the application. One of the most important causes of this contamination is the susceptibility of the species being cultivated surrounding sugar cane. In order to evaluate the effects of sugar cane plant ripeners trinexapac-ethyl and sulfometuron-methyl on peanuts, cotton, potato, coffee, citrus, beans, sunflower, cassava, rubber, soybean, and grapes, eleven experiments - one for each species - were carried out from May 2009 to Jan. 2010. The field experiment was set according to a completely random design with five treatments and four replications. Just before or during flowering, a single treatment of trinexapac-ethyl at 100 or 200 g ha-1 and sulfometuron-methyl at 7.5 or 15 g ha-1 was applied to plants. A control treatment (plants not treated) for each species was part of each experiment. Trinexapac, at the doses of 100 and 200 g ha-1, showed selectivity to peanuts, cotton, potato, coffee, citrus, sunflower, cassava, rubber, soybean, and grape. At the lowest dose (100 g ha-1), it was selective for bean. Sulfometuron, at the dose of 7.5 g ha-1, was selective for peanuts and, at the two studied doses (7.5 and 15 g ha-1), it was selective for coffee, citrus, cassava, and rubber.

Pathogenicity, colony morphology and diversity of isolates of Guignardia citricarpa and G-mangiferae isolated from Citrus spp.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Synthesis and physical properties of lipid-based poly(ester-urethane)s, I: Effect of varying polyester segment length

Four aliphatic thermoplastic poly(ester-urethane)s (PEUs) with similar molecular weights but varying polyesters molecular weight (534-1488 g/mol) were prepared from polyester diols, obtained by melt condensation of Azelaic acid and 1,9-Nonanediol, and 1,7-heptamethylene di-isocyanate (HPMDI) all sourced from vegetable oil feedstock. The thermal, and mechanical properties, and crystal structure of PEUs were investigated using DSC, TGA, DMA, tensile analysis and WAXD. For sufficiently long polyester chain, WAXD data indicated no hydrogen bonds polyethylene (PE)-like crystalline packing and for short polyester chains, small crystal domains with significant H-bonded polyamide (PA)-like packing. Crystallinity decreased with decreasing polyester molecular weights. The polymorphism of PEUs and consequently their melting characteristics were found to be largely controlled by polyester segment length. TGA of the PEUs indicated improved thermal stability with decreasing polyester chain length, suggesting a stabilization effect by urethane groups. Mechanical properties investigated by DMA and tensile analysis were found to scale predictably with the overall crystallinity of PEUs. (C) 2012 Elsevier Ltd. All rights reserved.

Alteração fisiológica da cana-de-açúcar pela aplicação de Glyphosate e Sulfumeturon-Methyl

O bloqueio parcial das rotas onde atuam os herbicidas, com uso de baixas doses, pode ter implicações importantes, como a alteração do balanço de processos metabólicos nas plantas. Assim, foi conduzido no ano agrícola 2006/2007 um experimento em cana-soca de segundo corte na Fazenda Jurema, pertencente ao grupo COSAN, município de Barra Bonita-SP, para verificar os efeitos do glyphosate e do sulfumeturon-methyl, em subdoses, no comportamento fisiológico da cana-de-açúcar pelos níveis de clorofila e carotenoides. Os tratamentos constituíram-se da aplicação de dois herbicidas: sulfumeturon-methyl (Curavial 360 e.a. kg-1) e glyphosate (Roundup 480 i.a. kg-1), isolados e em misturas, em diferentes doses, e um tratamento controle, sem a aplicação dos herbicidas. As doses utilizadas foram: glyphosate 200 mL p.c. ha-1; glyphosate 400 mL p.c. ha -1; glyphosate 200 mL p.c. ha -1 + 10 g p.c. ha-1 de sulfumeturon-methyl; glyphosate 150 mL p.c. ha -1 + 12 g p.c. ha -1 de sulfumeturon-methyl; e sulfumeturon-methyl 20 g p.c. ha -1. O delineamento experimental utilizado foi o de blocos casualizados, com quatro repetições. As avaliações foram realizadas 15 e 30 dias após o plantio (DAP) e 30, 60, 90, 120, 150 e 180 dias após a colheita (DAC). As folhas foram cortadas padronizando-se o mesmo peso e área foliar. Para determinação do conteúdo de clorofila e carotenoides, amostras de 0,2 g de tecido foliar fresco foram preparadas e os extratos filtrados, sendo efetuadas leituras em espectrofotômetro (663 e 645 nm para clorofilas a e b, respectivamente). A aplicação de glyphosate e sulfumeturon-methyl nas maiores doses interferiu no conteúdo de carotenoides quando estes foram comparados com a testemunha. A maior dose de glyphosate diminuiu significativamente o conteúdo de clorofilas e carotenoides na cana-de-açúcar, porém esse resultado não se manteve quando a dose foi reduzida para 200 mL p.c. ha-1 . Os teores de clorofila foram inversamente proporcionais aos níveis Fe. A aplicação de sulfumeturon-methyl não interferiu nos teores de clorofila, no entanto os níveis de carotenoides se mostraram mais sensíveis e seus teores reduzidos. As alterações observadas nos níveis de clorofilas e carotenoides pela aplicação dos produtos podem afetar de maneira distinta o metabolismo da fotossíntese pela absorção e/ou conversão de energia.

Ineficiência de acibenzolar-S-methyl na indução de resistência de feijoeiro comum à murcha-de-Curtobacterium

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Role of nitric oxide in the periaqueductal gray in defensive behavior in mice: influence of prior local N-methyl-D-aspartate receptor activation and aversive condition

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Crystal structure, DNA binding studies, nucleolytic property and topoisomerase I inhibition of zinc complex with 1,10-phenanthroline and 3-methyl-picolinic acid

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Characterization of castor oil based polyurethane films prepared with N-methyl-2-pyrrolidinone as a solvent

Molecular mobility in castor oil based polyurethane was investigated with thermally stimulated depolarization current (TSDC) measurements and alternating-current (ac) dielectric relaxation spectroscopy. Three peaks could be observed in TSDC thermograms from 173 to 373 K. The relaxation located at 213 K could be attributed to the change in the molecular chain due to the interaction between the isocyanate and the solvent, and it was well fitted with the Vogel-Fulcher-Tammann equation. The other two peaks were located at 274 and 365 K and could be attributed to interfacial polarization and space charge, respectively. (c) 2005 Wiley Periodicals, Inc.

Obtenção de biodiesel através da transesterificação do óleo de farelo de arroz utilizando KI/Al2O3

This study proposes to find a biodiesel through transesterification of rice bran oil with KI/Al2O3 checking the influence of two types of alumina (Amorphous and Crystalline) for conversion into methyl esters. The catalyst was synthesized by the wet impregnation method. Adding 30 mL of 35% KI(aq.) in 10 g of alumina, under stirring at 80 °C for 3 hours. The reaction conditions used in this study were optimized, with a molar ratio methanol:oil of 15:1, 8 h of reaction time and reflux temperature. The catalyst amount was varied in the range of 1 to 5 % wt. The solid catalysts materials were analyzed by: x-ray diffraction (XRD), thermogravimetry (TG), N2 adsorption/desorption, scanning electron microscopy (SEM) and basicity, for the identification of its structure and composition, verifying the presence of basic sites. The results showed that Al2O3(A) presents an amorphous structure, high surface area and a better catalytic activity, in relation to the catalyst synthesized with Al2O3(C) support that proved to have a more crystalline structure, having as well, a lesser surface area, enabling difficulties for the incorporation of active sites. The obtained biodiesel with 5% wt. KI/Al2O3(A) presented physicochemical properties within the standards specified by the Resolution No 7/2008 ANP and obtained the best reaction yield with 95.2%, according to quantitative measurement from the TG, which showed 96.2% conversion into methyl esters. It was furthermore found that with the increasing amount of the quantity of the catalyst in the reaction, there was also an increase in the ester content obtained. The specific mass and the kinematic viscosity were reduced with the increase of the amount of quantity of the catalyst, indicating an increase in the conversion of triglycerides