The electrochemical reduction of the purines guanine and adenine at platinum electrodes in several room temperature ionic liquids

The reduction of guanine was studied by microelectrode voltammetry in the room temperature ionic liquids (RTILs) N-hexyltriethylammonium bis (trifluoromethanesulfonyl) imide [N6,2,2,2][N(Tf)2], 1-butyl-3-methylimidazolium hexafluorosphosphate [C4mim][PF6], N-butyl-N-methyl-pyrrolidinium bis(trifluoromethanesulfonyl)imide [C4mpyrr][N(Tf)2], 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide [C4mim][N(Tf)2], N-butyl-N-methyl-pyrrolidinium dicyanamide [C4mpyrr][N(NC)2] and tris(P-hexyl)-tetradecylphosphonium trifluorotris(pentafluoroethyl)phosphate [P14,6,6,6][FAP] on a platinum microelectrode. In [N6,2,2,2][NTf2] and [P14,6,6,6][FAP], but not in the other ionic liquids studied, guanine reduction involves a one-electron, diffusion-controlled process at very negative potential to produce an unstable radical anion, which is thought to undergo a dimerization reaction, probably after proton abstraction from the cation of the ionic liquid. The rate of this subsequent reaction depends on the nature of the ionic liquid, and it is faster in the ionic liquid [P14,6,6,6][FAP], in which the formation of the resulting dimer can be voltammetrically monitored at less negative potentials than required for the reduction of the parent molecule. Adenine showed similar behaviour to guanine but the pyrimidines thymine and cytosine did not; thymine was not reduced at potentials less negative than required for solvent (RTIL) decomposition while only a poorly defined wave was seen for cytosine. The possibility for proton abstraction from the cation in [N6,2,2,2][NTf2] and [P14,6,6,6][FAP] is noted and this is thought to aid the electrochemical dimerization process. The resulting rapid reaction is thought to shift the reduction potentials for guanine and adenine to lower values than observed in RTILs where the scope for proton abstraction is not present. Such shifts are characteristic of so-called EC processes where reversible electron transfer is followed by a chemical reaction. © 2009 Elsevier B.V.

Efficacy of herbicides applied to Digitaria horizontalis plants under different water conditions

Este projeto objetivou relacionar a eficiência de controle de herbicidas inibidores da ACCase aplicados em pós-emergência em plantas de Digitaria horizontalis submetidas a diferentes teores de água no solo. Os experimentos foram conduzidos em casa de vegetação, com a aplicação de três diferentes herbicidas (fluazifop-p-butil, haloxyfop-methyl e sethoxydim + óleo mineral Assist). O delineamento experimental utilizado para cada herbicida foi inteiramente casualizado, com quatro repetições, constituído de um fatorial 3 x 4, sendo a combinação de três manejos hídricos (-0,03, 0,07 e -1,5 MPa) e quatro doses desses produtos (100, 50, 25 e 0% da dose recomendada). A aplicação dos herbicidas foi feita em dois estádios vegetativos: 4-6 folhas e 2-3 perfilhos. As avaliações visuais de fitotoxicidade foram realizadas aos 14 dias após a aplicação e avaliou-se a matéria seca das plantas ao final do estudo. A eficiência de controle não foi influenciada pelos manejos hídricos quando se aplicou a dose recomendada de todos os herbicidas na fase inicial de desenvolvimento das plantas (estádio de 4-6 folhas). em aplicações tardias (estádio de 2-3 perfilhos), as plantas mantidas sob estresse hídrico apresentaram menor fitotoxicidade.

Efeito de herbicidas sobre plantas de Brachiaria plantaginea submetidas a estresse hídrico

Este trabalho objetivou avaliar a eficiência de controle de herbicidas inibidores da ACCase aplicados em pós-emergência em plantas de Brachiaria plantaginea submetidas a diferentes teores de água no solo. O estudo foi conduzido em casa de vegetação. O delineamento experimental foi o inteiramente casualizado, com quatro repetições, utilizando-se o esquema fatorial 9 x 4, sendo a combinação de três manejos hídricos (-0,03, -0,07 e -1,5 MPa) com três herbicidas (fluazifop-p-butil, haloxyfop-methyl e sethoxydim + óleo mineral Assist) e quatro doses destes (100, 50, 25 e 0% da dose recomendada). A aplicação dos herbicidas foi realizada em dois estádios vegetativos das plantas: 4-6 folhas e 2-3 perfilhos. As avaliações visuais de fitointoxicação das plantas de B. plantaginea foram realizadas aos 3, 7 e 14 dias após a aplicação, sendo determinada a massa seca das plantas no final do experimento. A eficiência de controle foi menor em plantas mantidas em potencial de água no solo de -1,5 MPa (manejo hídrico de 8%), independentemente do herbicida utilizado, nos dois estádios de aplicação, com exceção do herbicida haloxyfop-methyl aplicado no estádio de 2-3 perfilhos. Não houve diferenças de controle entre as aplicações com 100 e 50% da dose recomendada dos herbicidas nas plantas no estádio de 4-6 folhas, independentemente do manejo hídrico.

Respostas de plantas de Eleusine indica sob diferentes condições hídricas a herbicidas inibidores da ACCase

Objetivou-se neste estudo avaliar a eficiência de controle de herbicidas inibidores da ACCase aplicados em pós-emergência em plantas de Eleusine indica submetidas a diferentes teores de água no solo. Os experimentos foram conduzidos em casa de vegetação, com a aplicação de três diferentes herbicidas (fluazifop-p-butil, haloxyfop-methyl e sethoxydim + óleo mineral Assist); o delineamento experimental utilizado para cada herbicida foi inteiramente casualizado, com quatro repetições, constituído de um fatorial 3 x 4, sendo a combinação de três manejos hídricos (-0,03, -0,07 e -1,5 MPa) e quatro doses desses produtos (100, 50, 25 e 0% da dose recomendada). Os parâmetros fisiológicos avaliados foram: taxa fotossintética, condutância estomática, transpiração, temperatura da folha e matéria seca das plantas. As avaliações visuais de fitotoxicidade foram realizadas aos 14 dias após a aplicação. Os manejos hídricos aplicados não influenciaram o controle das plantas nos tratamentos testados, com exceção do herbicida sethoxydim, que teve sua eficiência hídrica prejudicada quando da deficiência hídrica nas aplicações das doses fracionadas. A taxa fotossintética, a transpiração e a condutância estomática foram maiores em plantas submetidas ao manejo hídrico de 13%, as quais apresentaram as menores temperaturas foliares em relação à temperatura ambiente.

Effect of water stress on herbicide efficiency applied to Urochloa decumbens

M.R. Rocha-Pereira, A.E. Klar, D. Martins, G.S. Ferreira de Souza, and J. Villalba. 2012. Effect of water stress on herbicide efficiency applied to Urochloa decumbens. Cien. Inv. Agr. 39(1): 211-220. This project aimed to measure the control efficiency of Acctil Coenzime A Carboxilase (ACCase)-inhibiting herbicides post-emergence applied to Urochloa decumbens (Stapf) R.D. Webster under different soil water contents. The experiment was conducted in a greenhouse at the Department of Plant Production, Faculty of Agronomic Sciences, UNESP, Botucatu, Silo Paulo. The experimental design was a completely randomized design with four replications, consisting of a 9 x 4 factorial, combined with three water management systems (-0.03, -0.07 and -1.5 MPa) and three herbicides (fluazifop-p-butyl, haloxyfop-methyl and sethoxydim + oil using four doses (100, 50, 25 and 0% of the recommended dose). Herbicide applications were conducted at two vegetative stages for all species: a 4-6 leaf stage and a 2-3 tiller stage. The physiological parameters evaluated were as follows: photosynthetic rate, stomatal conductance, transpiration, leaf temperature and plant dry matter. The visual assessments of phytotoxicity were performed 28 days after herbicide application. The control efficiency was lower in plants grown under soil water potential conditions of -1.5 MPa, regardless of the herbicide used during the two application stages; however, none reached 100% control. Fractionation of the recommended herbicide doses reduced effectiveness, with the exception of the 50%-dose application of sethoxydim and fluazifop-p-butyl herbicides, which were also effective in the 4-6 leaf plant control under normal water conditions.

Potenciais hídricos no solo sobre a eficácia de herbicidas em plantas daninhas monocotiledôneas

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Herbicidas inibidores da ACCase em plantas de Cenchrus echinatus em estresse hídrico

This project aimed to relate the efficiency of control of ACCase inhibiting herbicides applied post-emergence in Cenchrus echinatus under different soil water contents. The experiments were conducted in a greenhouse, with the application of three different herbicides (fluazifop-p-butyl, haloxyfop-methyl and sethoxydim + oil Assist) and the experimental design for each herbicide was completely randomized design with four replications, consisting a 3 x 4 factorial, with the combination of water management strategies (-0.03, -0.07 and -1.5 MPa) and four doses of these products (100, 50, 25 and 0% of the recommended dose). Herbicide application was made at vegetative stage of 2-3 tillers. The water management strategies were initiated in the development stage of two leaves, replacing the water until the soil reaches the potential of -0.01 MPa, when it came to severe pre-determined for each water management. The physiological parameters evaluated were: photosynthetic rate, stomatal conductance, transpiration, leaf temperature and plant dry matter. The visual assessments of phytotoxicity were performed at 7, 14, 21 and 28 days after application. The efficiency of these herbicides was influenced by soil management and water lowest in plants grown in the minimal potential of water in the soil of -1.5 MPa. All the herbicides were unsatisfactory controls in applications late (2-3 tiller plants).

Influence of soil water potential in the action of herbicides on goosegrass (Eleusine indica (L) Gaertn)

Currently, the use of herbicides is essential in a practical and common in agricultural areas, but efficiency of these herbicides can be compromised when applied on plants that thrive in water deficit conditions, due to low uptake and translocation of the product. Therefore, the aim of this study was to compare the efficiency of control ACCase inhibiting herbicides applied post-emergence in plants of Eleusine indica under different soil water contents. The experiment was conducted in a greenhouse and the experimental design was completely randomized design with four replications, consisting of a 9x4 factorial, with the combination of three soil water potentials (-0.03, -0.07 and -1.5 MPa) three herbicides (fluazifop-p -butyl, haloxyfop-methyl and sethoxydim + oil) and four doses (0, 25, 50, and 100 % of the recommended dose). Herbicide application was made in plants in vegetative stage 2-3 tillers. The soil water potential was initiated in the development stage of two leaves, and the water was supplemented until the soil reaches the potential of -0.01 MPa, when it came to minimum pre-determined for each water management. The physiological parameters evaluated were: photosynthetic rate, stomatal conductance, transpiration leaf temperature and plant dry mass. The visual assessments of phytotoxicity were performed at 7 and 14 days after application. The herbicides behaved in different ways according to the used water management. In severe water stress conditions (soil moisture at 8%) only fluazifop-p-butyl herbicide achieved satisfactory control (> 90%) in E. indica plants.

Gestational and lactational exposition to Di-N-butyl-phthalate (DBP) increases inflammation and preneoplastic lesions in prostate of wistar rats after carcinogenic N-methyl-N-nitrosourea (MNU) plus testosterone protocol

In the present study, it was evaluated the susceptibility of prostatic lesions in male adult rats exposed to Di-N-butyl-phthalate during fetal and lactational periods and submitted to MNU plus testosterone carcinogenesis protocol. Pregnant females were distributed into four experimental groups: CN (negative control); CMNU (MNU control); TDBP100 (100 mg/kg of DBP); TDBP500 (500 mg/kg of DBP). Females from the TDBP groups received DBP, by gavage, from gestation day 15 (GD15) to postnatal day 21 (DPN21), while C animals received the vehicle (corn oil). CMNU, TDBP100, and TDBP500 groups received a single intraperitoneal injection of MNU (50 mg/kg) on the sixth postnatal week. After that, testosterone cypionate was administered subcutaneously two times a week (2 mg/kg) for 24 weeks. The animals were euthanized on PND220. Distal segment fragments of the ventral (VP) and dorsolateral prostate (DLP) were fixed and processed for histopathological analysis. Protein extracts from ventral prostate were obtained, and western blotting was performed to AR, ERα, MAPK (ERK1/2), and pan-AKT. Stereological analysis showed an increase in the epithelial compartment in TDBP100 and TDBP500 compared to CN. In general, there was increase in the incidence of inflammation and metaplasia/dysplasia in the DBP-treated groups, mainly in DLP, compared to CN and CMNU. Proliferation index was significant higher in TDBP500 and PIN (prostatic intraepithelial neoplasia) was more frequent in this group compared to CMNU. Western blot assays showed an increase in the expressions of AR and MAPK (ERK1/2) in the TDBP100 compared to CN, and ERα and AKT expressions were higher in the TDBP500 group compared do CN. These results showed that different doses of DBP during prostate organogenesis in Wistar rats could increase the incidence of premalignant lesions in initiated rats inducing distinct biological responses in the adulthood. © 2015 Wiley Periodicals, Inc. Environ Toxicol, 2015.

Computational analysis and physico-chemical characterization of an inclusion compound between praziquantel and methyl-beta-cyclodextrin for use as an alternative in the treatment of schistosomiasis

Schistosomiasis is still an endemic disease in many regions, with 250 million people infected with Schistosoma and about 500,000 deaths per year. Praziquantel (PZQ) is the drug of choice for schistosomiasis treatment, however it is classified as Class II in the Biopharmaceutics Classification System, as its low solubility hinders its performance in biological systems. The use of cyclodextrins is a useful tool to increase the solubility and bioavailability of drugs. The aim of this work was to prepare an inclusion compound of PZQ and methyl-beta-cyclodextrin (MeCD), perform its physico-chemical characterization, and explore its in vitro cytotoxicity. SEM showed a change of the morphological characteristics of PZQ:MeCD crystals, and IR data supported this finding, with changes after interaction with MeCD including effects on the C-H of the aromatic ring, observed at 758 cm(-1). Differential scanning calorimetry measurements revealed that complexation occurred in a 1:1 molar ratio, as evidenced by the lack of a PZQ transition temperature after inclusion into the MeCD cavity. In solution, the PZQ UV spectrum profile in the presence of MeCD was comparable to the PZQ spectrum in a hydrophobic solvent. Phase solubility diagrams showed that there was a 5.5-fold increase in PZQ solubility, and were indicative of a type A(L) isotherm, that was used to determine an association constant (K(a)) of 140.8 M(-1). No cytotoxicity of the PZQ:MeCD inclusion compound was observed in tests using 3T3 cells. The results suggest that the association of PZQ with MeCD could be a good alternative for the treatment of schistosomiasis.

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.

Effect of acibenzolar-S-methyl and Saccharomyces cerevisiae on the activation of Eucalyptus defences against rust

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

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)

Seletividade de herbicidas aplicados nas gramas Santo Agostinho e Esmeralda

Objetivou-se neste trabalho avaliar a seletividade de herbicidas aplicados nas gramas Santo Agostinho (Stenotaphrum secundatum) e Esmeralda (Zoysia japonica) em condições de campo. O delineamento experimental utilizado foi o de blocos casualizados, com quatro repetições. As gramas foram cortadas a 3 cm de altura e, em seguida, foram feitas as aplicações dos herbicidas. Os tratamentos utilizados foram: testemunha sem aplicação, fluazifop-p-butil (125 g ha-1), sethoxydim+óleo mineral (276 g ha-1 + 0,5% v v-1 de Assist), bispyribac-sodium (25 g ha-1), chlorimuron-ethyl (15 g ha-1), ethoxysulfuron (150 g ha-1), halosulfuron (112,5 g ha-1), iodosulfuron-methyl (10 g ha-1), metsulfuron-methyl (2,4 g ha-1), nicosulfuron (125 g ha-1), pyrithiobac-sodium (140 g ha-1), trifloxysulfuron-sodium (22,5 g ha-1), 2,4-D (720 g ha-1), quinclorac (375 g ha-1), atrazina (1.250 g ha-1), bentazon (600 g ha-1), linuron (1.350 g ha-1), fomesafen (187,5 g ha-1), lactofen (120 g ha-1), oxadiazon (600 g ha-1) e oxyfluorfen (720 g ha-1). Os herbicidas que apresentaram potencial de seletividade para o gramado de S. secundatum foram: os inibidores da ALS chlorimuron-ethyl, ethoxysulfuron, halosulfuron, iodosulfuron-methyl e metsulfuron-methyl, o mimetizador de auxina 2,4-D, os inibidores do fotossistema II atrazina e bentazon, bem como os inibidores da Protox fomesafen, lactofen e o oxadiazon. Para o gramado de Z. japonica, os herbicidas que apresentaram potencial de seletividade foram: os inibidores da ALS chlorimuron-ethyl, ethoxysulfuron, halosulfuron, metsulfuron-methyl e nicosulfuron, os mimetizadores de auxina 2,4-D e quinclorac, os inibidores do fotossistema II atrazina e bentazon, além dos inibidores da Protox fomesafen, lactofen e o oxadiazon.