Evaluation of the acute and sublethal toxicity of Mancozeb in Pacamã (Lophiosilurus alexandri).

The toxic potential of dithiocarbamates fungicides widely used in world agriculture is well known, among which Mancozeb is one of the most used. This study aimed to evaluate the toxicity of Mancozeb, determining the LC50% of the product and the behavioral and histological changes observed in fish of the Pacamã species through acute and sublethal toxicity tests. The first experiment was carried out on Pacamã fingerlings exposed to dosages of 0.5, 1, 2, 4, and 8mg/L of Mancozeb under the form ManzateWG®, for a total period of 96 hours in the acute experiment, and in the second experiment, fish were subjected to concentrations of 1/10 of those used in the acute experiment (0.05, 0.1, 0.2, 0.4 and 0.8mg/L, respectively), for 15 days in total. The 50% lethal concentration of ManzateWG® was calculated at the end of the acute experiment, presenting a value of 2.29mg/L at 96h for Pacamã fingerlings. A behavioral assessment was carried out through daily observation of the fish during both experiments, and an increase in mucus production was observed, as well as atypical social behavior in those exposed to the toxic agent. Histopathological evaluation was performed on livers collected after the end of the sublethal experiment, and the main hepatic alterations observed were cytoplasmic vacuolization, inflammatory infiltrate, and necrosis. Mancozeb has toxic potential and is capable of generating behavioral changes, as well as increasing the risk of liver damage in Pacamãs exposed to this compound.

Toxicidade aguda e risco ecotoxicológico do inseticida tiametoxam para alevinos de tilápia-do-nilo / Acute toxicity and ecotoxicological risk of thiamethoxam insecticide in nile tilapia fingerlings

O tiametoxam é um inseticida neonicotinóide usado em diversas culturas e classificado como perigoso para o meio ambiente.O objetivo do presente trabalho foi avaliar a toxicidade aguda do inseticida, por meio da determinação da CL50%, e o risco ecotoxicológico com mensuração da concentração ambiental estimada (CAE) e do quociente de risco (QR). O experimento foi realizado com alevinos de tilápias expostas a 150, 300, 450, 600 e 750mg/L de Actara(R) WG por um período total de 96 horas. O oxigênio dissolvido, o pH e a temperatura foram mensurados diariamente em todos os aquários. Nos grupos experimentais, houve uma variação dos valores de pH e de OD para as diferentes concentrações do inseticida. A CL50% 96h do Actara(R) para alevinos de tilápia foi de 322,08ppm. O quociente de risco (QR) variou de baixo a alto, de acordo com a metodologia usada.(AU)

The neonicotinoid insecticide thiamethoxam is used in different cultures and classified as dangerous for the environment. The aim of this study was to evaluate the acute toxicity of thiamethoxam by determining the lethal concentration (LC50) and ecotoxicological risk through Estimated Environmental Concentration (EEC) and Risk Quotient (RQ) measurement. The assays were done with Tilapia fingerlings exposed to 150, 300, 450, 600 and 750mg / L Actara WG during 96 hours. Dissolved oxygen, pH and temperature were measured daily in all aquariums. Dissolved oxygen and pH varied in the experimental groups. The LC50 Actara(R); 96h was 322.08ppm. The risk quotient (RQ) ranged from low to high according to the methodology used.(AU)

Silicon supported lipid-DNA thin film structures at varying temperature studied by energy dispersive X-ray diffraction and neutron reflectivity.

Non-viral gene transfection by means of lipid-based nanosystems, such as solid supported lipid assemblies, is often limited due to their lack of stability and the consequent loss of efficiency. Therefore not only a detailed thermo-lyotropic study of these DNA-lipid complexes is necessary to understand their interaction mechanisms, but it can also be considered as a first step in conceiving and developing new transfection biosystems. The aim of our study is a structural characterization of 1,2-dioleoyl-sn-glycero-3-phosphatidylcholine (DOPC)-dimethyl-dioctadecyl-ammonium bromide (DDAB)-DNA complex at varying temperature using the energy dispersive X-ray diffraction (EDXD) and neutron reflectivity (NR) techniques. We have shown the formation of a novel thermo-lyotropic structure of DOPC/DDAB thin film self-organized in multi-lamellar planes on (100)-oriented silicon support by spin coating, thus enlightening its ability to include DNA strands. Our NR measurements indicate that the DOPC/DDAB/DNA complex forms temperature-dependent structures. At 65°C and relative humidity of 100% DNA fragments are buried between single lamellar leaflets constituting the hydrocarbon core of the lipid bilayers. This finding supports the consistency of the hydrophobic interaction model, which implies that the coupling between lipid tails and hypo-hydrated DNA single strands could be the driving force of DNA-lipid complexation. Upon cooling to 25°C, EDXD analysis points out that full-hydrated DOPC-DDAB-DNA can switch in a different metastable complex supposed to be driven by lipid heads-DNA electrostatic interaction. Thermotropic response analysis also clarifies that DOPC has a pivotal role in promoting the formation of our observed thermophylic silicon supported lipids-DNA assembly.

Biomarcadores histológicos: toxicidade crônica pelo Roundup em piauçu (Leporinus macrocephalus) / Histological biomarkers: chronic toxicity for roundup in piauçu (Leporinus macrocephalus)

Avaliou-se o uso de brânquias, fígado e rins como biomarcadores histológicos em ensaio de toxicidade crônica com o herbicida Roundup® em piauçu (Leporinus. macrocephalus). Para tanto, os animais foram expostos a 1,58mg/L, dose equivalente a 1/10 da CL50 para a espécie por 14 e 28 dias, sendo utilizados cinco animais por tratamento correspondentes aos dias 0, 14 e 28. Hemorragia e necrose hepática e congestão renal foram as alterações que apresentaram diferenças entre os animais expostos e os não expostos. Dentre os órgãos usados como biomarcadores histopatológicos, o fígado foi o que apresentou os melhores resultados, seguido pelo rim.

The use of gills, liver, and kidneys as histological biomarkers was evaluated in a chronic toxicity analysis with herbicide Roundup® in piauçu (Leporinus macrocephalus). The animals were exposed to 1/10 of LC50 (1.58mg/L), during a period of 14 and 28 days. Five animals were used for treatment (days 0, 14, and 28). Hepatic hemorrhage and necrosis and renal congestion were the alterations that presented differences between exposed and non-exposed animals. Among the organs used as histological biomarkers, the liver presented the best results, followed by the kidneys.

New mode of coordination for the dinitrogen ligand: formation, bonding, and reactivity of a tantalum complex with a bridging N(2) unit that is both side-on and end-on.

The reaction of a mixture of 1 equiv of PhPH(2) and 2 equiv of PhNHSiMe(2)CH(2)Cl with 4 equiv of Bu(n)Li followed by the addition of THF generates the lithiated ligand precursor [NPN]Li(2).(THF)(2) (where [NPN] = PhP(CH(2)SiMe(2)NPh)(2)). The reaction of [NPN]Li(2).(THF)(2) with TaMe(3)Cl(2) produces [NPN]TaMe(3), which reacts under H(2) to yield the diamagnetic dinuclear Ta(IV) tetrahydride ([NPN]Ta)(2)(mu-H)(4). This hydride reacts with N(2) with the loss of H(2) to produce ([NPN]Ta(mu-H))(2)(mu-eta(1):eta(2)-N(2)), which was characterized both in solution and in the solid state, and contains strongly activated N(2) bound in the unprecedented side-on end-on dinuclear bonding mode. A density functional theory calculation on the model complex [(H(3)P)(H(2)N)(2)Ta(mu-H)](2)(mu-eta(1):eta(2)-N(2)) provides insight into the molecular orbital interactions involved in the side-on end-on bonding mode of dinitrogen. The reaction of ([NPN]Ta(mu-H))(2)(mu-eta(1):eta(2)-N(2)) with propene generates the end-on bound dinitrogen complex ([NPN]Ta(CH(2)CH(2)CH(3)))(2)(mu-eta(1):eta(1)-N(2)), and the reaction of [NPN]Li(2).(THF)(2) with NbCl(3)(DME) generates the end-on bound dinitrogen complex ([NPN]NbCl)(2)(mu-eta(1):eta(1)-N(2)). These two end-on bound dinitrogen complexes provide evidence that the bridging hydride ligands are responsible for the unusual bonding mode of dinitrogen in ([NPN]Ta(mu-H))(2)(mu-eta(1):eta(2)-N(2)). The dinitrogen moiety in the side-on end-on mode is amenable to functionalization; the reaction of ([NPN]Ta(mu-H))(2)(mu-eta(1):eta(2)-N(2)) with PhCH(2)Br results in C-N bond formation to yield [NPN]Ta(mu-eta(1):eta(2)-N(2)CH(2)Ph)(mu-H)(2)TaBr[NPN]. Nitrogen-15 NMR spectral data are provided for all the tantalum-dinitrogen complexes and derivatives described.

Fluxional behavior of the dinitrogen ligand 2,9-dimethyl-1,10-phenanthroline in cationic methyl platinum(II) complexes.

The ionic methylplatinum(II) complexes [Pt(Me)(L)(dmphen)]X (dmphen = 2,9-dimethyl-1,10-phenanthroline, L = Me(2)SO, X = PF(6)(-) 1a, BF(4)(-) 1b, CF(3)SO(3)(-) 1c, ClO(4)(-) 1d, B(C(6)H(5))(4)(-) 1e, [B(3,5-(CF(3))(2)C(6)H(3))(4)](-) 1f; L = n-Bu(2)SO, X = CF(3)SO(3)(-) 1g; L = PPh(3), X = PF(6)(-) 2a, BF(4)(-) 2b, CF(3)SO(3)(-) 2c, ClO(4)(-) 2d, B(C(6)H(5))(4)(-) 2e, [B(3,5-(CF(3))(2)C(6)H(3))(4)](-) 2f; X = CF(3)SO(3)(-), L = CyNH(2) 3a, i-PrNH(2) 3b, 2,6-Me(2)py 3c, EtNH(2) 3d, AsPh(3) 3e, dimethylthiourea (Me(2)th) 3f and the uncharged [Pt(Me)(X)(dmphen)] (X = SCN(-) 4a, SeCN(-) 4b) complexes have been synthesized and fully characterized. In chloroform, as well as in acetone or methanol, complexes 1a-1g, 2a-2h (X = Cl(-) g, NO(2)(-) h, formed "in situ"), and 3e show dynamic behavior due to the oscillation of the symmetric chelating ligand dmphen between nonequivalent bidentate modes. All the other compounds feature a static structure in solution. The crystal structure of 2a shows a tetrahedral distortion of the square planar coordination geometry, a loss of planarity of the dmphen ligand, and, most notably, a rotation of the dmphen moiety, around the N1-N2 vector, to form a dihedral angle of 42.64(8) degrees with the mean coordination plane. The hexafluorophosphate ion lies on the side of the phenanthroline ligand. The interionic structures of 2a, 2b, and 2f were investigated in CDCl(3) at low temperature by (1)H-NOESY and (19)F[(1)H]-HOESY NMR spectroscopies. Whereas PF(6)(-) (2a) and BF(4)(-) (2b) show strong contacts with the cation [Pt(Me)(PPh(3))(dmphen)](+), being located preferentially on the side of the phenanthroline ligand, the [B(3,5-(CF(3))(2)C(6)H(3))(4)](-) (2f) ion does not form a tight ion pair. The dynamic process was studied by variable-temperature NMR spectroscopy for 1a-1f and 2a-2h in CDCl(3). The activation energies DeltaG(298) for the sulfoxide complexes 1a-1f are lower than those of the corresponding phosphine complexes 2a-2f by approximately 10 kJ mol(-)(1). The nature of the counteranion exerts a tangible influence on the fluxionality of dmphen in both series of complexes 1 and 2. The sequence of energies observed for 2a-2h encompasses an overall difference of about 16 kJ mol(-)(1), increasing in the order Cl(-) approximately NO(2)(-) << CF(3)SO(3)(-) < ClO(4)(-) < B(C(6)H(5))(4)(-) < BF(4)(-) approximately PF(6)(-) < B(3,5-(CF(3))(2)C(6)H(3))(4)(-). Acetone and methanol have an accelerating effect on the flipping. Concentration-dependent measurements, carried out in CDCl(3) for 2a with n-Bu(4)NPF(6) and the ligands dmphen, n-Bu(2)SO, sec-Bu(2)SO, and sec-Bu(2)S showed that the rate of the fluxional motion is unaffected by added n-Bu(4)NPF(6), whereas in the other cases this increases linearly with increasing ligand concentration, according to a pattern of behavior typical of substitution reactions. Dissociative and associative mechanisms can be envisaged for the observed process of flipping. Dissociation can be prevalent within the ion pair formed by a "noncoordinating" anion with the metallic cationic complex in chloroform. Among the possible associative mechanisms, promoted by polar solvents or by relatively strong nucleophiles, a consecutive displacement mechanism is preferred to intramolecular rearrangements of five-coordinate intermediates.

Structures of furanosides: geometrical analysis of low-temperature X-ray and neutron crystal structures of five crystalline methyl pentofuranosides.

Crystal structures of all five crystalline methyl D-pentofuranosides, methyl alpha-D-arabinofuranoside (1), methyl beta-D-arabinofuranoside (2), methyl alpha-D-lyxofuranoside (3), methyl beta-D-ribofuranoside (4) and methyl alpha-D-xylofuranoside (5) have been determined by means of cryogenic X-ray and neutron crystallography. The neutron diffraction experiments provide accurate, unbiased H-atom positions which are especially important because of the critical role of hydrogen bonding in these systems. This paper summarizes the geometrical and conformational parameters of the structures of all five crystalline methyl pentofuranosides, several of them reported here for the first time. The methyl pentofuranoside structures are compared with the structures of the five crystalline methyl hexopyranosides for which accurate X-ray and neutron structures have been determined. Unlike the methyl hexopyranosides, which crystallize exclusively in the C(1) chair conformation, the five crystalline methyl pentofuranosides represent a very wide range of ring conformations.

Synthesis, molecular modeling, and opioid receptor affinity of 9, 10-diazatricyclo[4.2.1.1(2,5)]decanes and 2,7-diazatricyclo[4.4.0. 0(3,8)]decanes structurally related to 3,8-diazabicyclo[3.2. 1]octanes.

Various lines of evidence, including molecular modeling studies, imply that the endoethylenic bridge of 3,8-diazabicyclo[3.2. 1]octanes (DBO, 1) plays an essential role in modulating affinity toward mu opioid receptors. This hypothesis, together with the remarkable analgesic properties observed for N(3) propionyl, N(8) arylpropenyl derivatives (2) and of the reverted isomers (3), has prompted us to insert an additional endoethylenic bridge on the piperazine moiety in order to identify derivatives with increased potency toward this receptor class. In the present report, we describe the synthesis of the novel compounds 9,10-diazatricyclo[4.2. 1.1(2,5)]decane (4) and 2,7-diazatricyclo[4.4.0.0(3,8)]decane (5), as well as the representative derivatives functionalized at the two nitrogen atoms by propionyl and arylpropenyl groups (6a-e, 7a-d). Opioid receptor binding assays revealed that, among the compounds tested, the N-propionyl-N-cinnamyl derivatives 6a and 7a exhibited the highest mu-receptor affinity, and remarkably, compound 7a displayed in vivo (mice) an analgesic potency 6-fold that of morphine.