Syntheses, crystal structure and theoretical investigation of novel heteroleptic complexes of nickel(II) with N-R-sulfonyldithiocarbimate and phosphine ligands

Five new complexes of general formula: [Ni(RSO(2)N=CS(2))(dppe)], where R = C(6)H(5) (1), 4-ClC(6)H(4) (2), 4-BrC(6)H(4) (3), 4-IC(6)H(4) (4) and dppe = 1,2-bis(diphenylphosphino) ethane and [Ni(4-IC(6)H(4)SO(2)N=CS(2))(PPh(3))(2)] (5), where PPh3 = triphenylphosphine, were obtained in crystalline form by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate K(2)(RSO(2)N=CS(2)) and dppe or PPh(3) with nickel(II) chloride in ethanol/water. The elemental analyses and the IR, (1)H NMR, (13)C NMR and (31)P NMR spectra are consistent with the formation of the square planar nickel(II) complexes with mixed ligands. All complexes were also characterized by X-ray diffraction techniques and present a distorted cis-NiS(2)P(2) square-planar configuration around the Ni atom. Quantum chemical calculations reproduced the crystallographic structures and are in accord with the spectroscopic data. Rare C-H center dot center dot center dot Ni intramolecular short contact interactions were observed in the complexes 1-5. (C) 2011 Elsevier B. V. All rights reserved.

Effect of SO(2) on the Transport Properties of an Imidazolium Ionic Liquid and Its Lithium Solution

Transport coefficients have been measured as a function of the concentration of sulfur dioxide, SO(2), dissolved in 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)-imide, [BMMI][Tf(2)N], as well as in its lithium salt solution, Li[Tf(2)N]. The SO(2) reduces viscosity and density and increases conductivity and diffusion coefficients in both the neat [BMMI] [Tf(2)N] and the [BMMI][Tf(2)N]-Li[Tf(2)N] solution. The conductivity enhancement is not assigned to a simple viscosity effect; the weakening of ionic interactions upon SO(2) addition also plays a role. Microscopic details of the SO(2) effect were unraveled using Raman spectroscopy and molecular dynamics (MD) simulations. The Raman spectra suggest that the Li(+)-[Tf(2)N] interaction is barely affected by SO(2), and the SO(2)-[Tf(2)N] interaction is weaker than previously observed in an investigation of an ionic liquid containing the bromide anion. Transport coefficients calculated by MD simulations show the same trend as the experimental data with respect to SO(2) content. The MD simulations provide structural information on SO(2) molecules around [Tf(2)N], in particular the interaction of the sulfur atom of SO(2) with oxygen and fluorine atoms of the anion. The SO(2)-[BMMI] interaction is also important because the [BMMI] cations with above-average mobility have a larger number of nearest-neighbor SO(2) molecules.

Characterization of anodic silicon oxide films grown in room temperature ionic liquids

The electroformation of silicon oxide was performed in two room temperature ionic liquids (RTIL), 1-butyl-3-methyl-imidazolium bis(trifluoromethane sulfonyl) imide (BMITFSI) and N-n-butyl-N-methylpiperidinium bis(trifluoromethane sulfonyl) imide (BMPTFSI). This phenomenon was studied by electrochemical techniques and it was observed that the oxide growth follows a high-field mechanism. X-ray Photoelectron Spectroscopy experiments have shown that a non-stoichiometric oxide film was formed, related to the low water content present in both RTILs (< 30 ppm). The roughness values obtained by using AFM technique of the silicon surface after etching with HF was 1.5 nm (RMS). The electrochemical impedance spectroscopy at low frequencies range was interpreted as a resistance in parallel with a CPE element, the capacitance obtained was associated with the dielectric nature of the oxide formed and the resistance was interpreted considering the chemical dissolution of the oxide by the presence of the TFSI anion. The CPE element was associated with the surface roughness and the very thin oxide film obtained. (C) 2007 Elsevier Ltd. All rights reserved.

Shielding of ionic interactions by sulfur dioxide in an ionic liquid

The effect of adding SO(2) on the structure and dynamics of 1-butyl-3-methylimidazolium bromide (BMIBr) was investigated by low-frequency Raman spectroscopy and molecular dynamics (MD) simulations. The MD simulations indicate that the long-range structure of neat BMIBr is disrupted resulting in a liquid with relatively low viscosity and high conductivity, but strong correlation of ionic motion persists in the BMIBr-SO(2) mixture due to ionic pairing. Raman spectra within the 5 < omega < 200 cm(-1) range at low temperature reveal the short-time dynamics, which is consistent with the vibrational density of states calculated by MD simulations. Several time correlation functions calculated by MD simulations give further insights on the structural relaxation of BMIBr-SO(2).

Electrostatic layer-by-layer deposition and electrochemical characterization of thin films composed of MnO(2) nanoparticles in a room-temperature ionic liquid

Thin films of MnO(2) nanoparticles were grown using the layer-by-layer method with poly (diallyldimetylammonium) as the intercalated layer. The film growth was followed by UV-vis, electrochemical quartz crystal microbalance (EQCM), and atomic force microscopy. Linear growth due to electrostatic immobilization of layers was observed up to 30 bilayers, but electrical connectivity was maintained only for 12 MnO(2)/PPDA bilayers. The electrochemical characterization of this film in 1-butyl-2,3-dimethyl-imidazolium (BMMI) bis(trifluoromethanesulfonyl)imide (TFSI) (BMMITFSI) with and without addition of a lithium salt indicated a higher electrochemical response of the nanostructured electrode in the lithium-containing electrolyte. On the basis of EQCM experiments, it was possible to confirm that the charge compensation process is achieved mainly by the TFSI anion at short times (<2 s) and by BMMI and lithium cations at longer times. The fact that large ions like TFSI and BMMI participate in the electroneutrality is attributed to the redox reaction that occurs at the superficial sites and to the high concentration of these species compared to that of lithium cations.

Transport coefficients, Raman spectroscopy, and computer simulation of lithium salt solutions in an ionic liquid

Lithium salt solutions of Li(CF3SO2)(2)N, LiTFSI, in a room-temperature ionic liquid (RTIL), 1-butyl-2,3-dimethyl-imidazolium cation, BMMI, and the (CF3SO2)(2)N-, bis(trifluoromethanesulfonyl)imide anion, [BMMI][TFSI], were prepared in different concentrations. Thermal properties, density, viscosity, ionic conductivity, and self-diffusion coefficients were determined at different temperatures for pure [BMMI][TFSI] and the lithium solutions. Raman spectroscopy measurements and computer simulations were also carried out in order to understand the microscopic origin of the observed changes in transport coefficients. Slopes of Walden plots for conductivity and fluidity, and the ratio between the actual conductivity and the Nernst-Einstein estimate for conductivity, decrease with increasing LiTFSI content. All of these studies indicated the formation of aggregates of different chemical nature, as it is corroborated by the Raman spectra. In addition, molecular dynamics (MD) simulations showed that the coordination of Li+ by oxygen atoms of TFSI anions changes with Li+ concentration producing a remarkable change of the RTIL structure with a concomitant reduction of diffusion coefficients of all species in the solutions.

Formation and decomposition of N-alkyinaphthalimides: experimental evidences and ab initio description of the reaction pathways

The kinetics of hydrolysis of 1,8-N-butyl-naphthalimide (1,8-NBN) to 1,8-N-butyl-naphthalamide (1,8-NBAmide) and of 2,3-N-butyl-naphthalimide (2,3-NBN) to 2,3-N-butyl-naphthalamide (2,3-NBAmide), as well as the formation of the respective anhydrides from the amides were investigated in a wide acidity range. 1,8-NBN equilibrates with 1,8-NBAmide in mild alkali. Under the same conditions 2,3-NBN quantitatively yields 2,3-NBAmide. Over a wide range of acidities the reactions of the 1,8- and 2,3-N-butyl-naphthalamides (or imides) yield similar products but with widely different rates and at distinct pH`s. Anhydride formation in acid was demonstrated for 1,8-NBAmide. The reactions mechanisms were rationalized in the manifold pathways of ab initio calculations. The differences in rates and pH ranges in the reactions of the 1,8- and 2,3-N-butyl-naphthalamides were attributed to differences in the stability of the tetrahedral intermediates in alkali as well as the relative stabilities of the five and six-membered ring intermediates. The rate of carboxylic acid assisted 1,8-N-Butyl-naphthalamide hydrolysis is one of the largest described for amide hydrolysis models. Copyright (C) 2010 John Wiley & Sons, Ltd.

Reações do algodoeiro CNPA-ITA 90 ao cloreto de mepiquat

Com o objetivo de avaliar os efeitos de diferentes doses de cloreto de mepiquat aplicadas parceladamente no algodoeiro (Gossypium hirsutum L.) cv. CNPA-ITA 90, dois experimentos foram conduzidos durante os anos agrícolas de 1993/94 e 1994/95, na Fazenda Itamarati, Ponta Porã, MS. As doses estudadas foram: 1) 0,0; 2) 12,5+12,5+25,0 (50,0); 3) 25,0+25,0+25,0 (75,0); 4) 0,0+ 50,0+50,0 (100,0) e 5) 12,5+62,5+50,0 (125,0) g ha-1 de cloreto de mepiquat. O delineamento experimental utilizado foi o de blocos casualizados, com quatro repetições. As aplicações foram efetuadas aos 34, 47 e 62 dias após a emergência (DAE), em 1993/94, e aos 42, 60 e 73 DAE no ano de 1994/95, quando as plantas apresentavam altura média de 51, 84 e 93 cm e 61, 79 e 97 cm, respectivamente. Com o aumento da dose de cloreto de mepiquat, verificou-se redução da altura de plantas, da matéria seca foliar, do caule e do total da parte vegetativa, do número de nós, de ramos, do comprimento de ramos, do número de frutos danificados e do número de maçãs, e aumento do número de capulhos totalmente abertos.

Reguladores vegetais na conservação pós-colheita de goiabas 'Paluma'

Avaliaram-se os efeitos da aplicação exógena de solução de ácido giberélico (GA), 6-benzilaminopurina (6-BAP) ou ácido indol-3-acético (IAA) a 100 ou 200 mg L-1 e de CaCl2 a 1% ou 2%, na conservação pós-colheita de goiabas-'Paluma', por infiltração a vácuo (500 mmHg.20 minutos-1). Os frutos tratados foram armazenados ao ambiente (21,6ºC, 73,4% UR) e analisados, periodicamente, física e quimicamente. Os tratamentos com cloreto de cálcio a 1% ou 2% foram os melhores na conservação destas goiabas, pois propiciou-lhes vida útil comercial de 7 dias, o que corresponde a aumento de um dia na vida de prateleira, quando comparados com os demais tratamentos. Os tratamentos utilizados não apresentaram efeitos significativos na evolução da coloração e da firmeza dos frutos durante o amadurecimento.

Reguladores de crescimento vegetal na concentração de macronutrientes em videira Itália

Em clima tropical semi-árido, o uso de reguladores vegetais em fruteiras permite o manejo do crescimento vegetativo, tão necessário ao escalonamento da produção e ao aumento da fertilidade das gemas. Estas substâncias influenciam vários fenômenos fisiológicos relacionados com a absorção mineral, como a condutância de membrana e utilização metabólica de íons. O objetivo deste trabalho foi avaliar o crescimento vegetativo, produção de matéria seca dos ramos, concentração e quantidade acumulada de N, P, K, Ca e Mg nos ramos e nos pecíolos e produção de panículas florais em resposta ao uso de reguladores vegetais, em plantas de videira da cultivar Itália. No experimento foram avaliados três ciclos vegetativos e cinco tratamentos (controle, chlormequat - 1500 mg L-1; daminozide - 3000 mg L-1; uniconazole - 30 mg L-1 e cloreto de mepiquat - 300 mg L-1), aplicados nas plantas em pulverizações aos 35 e 70 dias após a poda. Com o chlormequat e o uniconazole ocorreu efeito cumulativo nas plantas, quando aplicados em ciclos sucessivos da cultura, favorecendo o acúmulo de nutrientes e a diferenciação de gemas férteis em comparação com as plantas controle das videiras 'Itália'. Embora o daminozide tenha inibido significativamente o crescimento das plantas, não resultou em maior acúmulo de nutrientes e emissão de panículas florais nas plantas tratadas.

Importância do fluxo de massa e difusão no suprimento de potássio ao algodoeiro como variável de água e potássio no solo

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Produtividade e composição bromatológica do capim-Tobiatã com adubação NPK

Productivity and nutritional quality of Tobiata grass as a function of NPK fertilization. The present study had as objective to study five N rates (0, 50, 100, 150 and 200 kg ha(-1)), two P(2)O(5) rates (96 and 30 kg ha(-1)) as superphosphate triple, and two doses of K(2)O (170 and 143 kg ha(-1)) as potassium chloride, in the forage Panicum maximum cv. Tobiata, with irrigation. The experiment was conducted using a randomized blocks design with four replicates. In the implantation of the experiment, P and K were applied based on theoretical doses required to reach values of 40 mg dm(-3) of P and K 5% of CTC. After three cuts, dry mass produced by the forage was estimated in order to obtain the values of the nutrients exported by the plant. Only after this procedure did the application of the doses of N take place. The production of dry mass - DM, crude protein - CP, neutral-detergent fiber - NDF, and acid-detergent fiber - ADF, were influenced by cuts; increasing N fertilization increased the production of DM, CP and decreased ADF and NDF, providing better forage quality. The fertilization with phosphorus and potassium can be done based on DM production or P and K content in soil.

Influências de dietas ricas em ácidos graxos saturados e insaturados sobre o miocárdio de ratos

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

Effect of Ionic Liquid on the Determination of Aromatic Amines as Contaminants in Hair Dyes by Liquid Chromatography Coupled to Electrochemical Detection

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

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.