We compared environmental influences on the assemblages of stream fishes of contiguous but biogeographically distinct parts of the Upper Paraguay and Paraná basins in Brazil, aiming to describe the ...main distribution patterns of fish species in the headwater streams. We analyzed bimonthly samples in 10 streams in each basin from January to November 2004. Sixty fish species were collected, including 40 species in streams of the Paraguay Basin and 42 species in streams of the Paraná Basin. The species abundance rank did not differ between the basins. We found a clear differentiation between the Paraguay and Paraná stream fish assemblages. There were significant differences in species composition among streams, but no seasonal differences in species composition. Connectivity between streams explains the differences in species composition for the Paraguay streams, but not for the Paraná streams. Hydrological characteristics were the main factors determining species distribution in both basins, suggesting that the migratory capacity of each species and biogeographical barriers may act to filter the local species composition from the total species pool of colonizers.
1,6-Dimethyl-4-hydroxy-3-pyridinecarboxylic acid (DQ716) and 4-hydroxy-2-methyl-3-pyridinecarboxylic acid (DQ2) were evaluated for possible application to iron (Fe) and aluminium (Al) chelation ...therapy. Metal/ligand solution chemistry, electrochemistry, cytotoxicity, octanol/water partitioning (D(o/w)), and chelation efficiency, were studied. The Fe(iii)/DQ716, Fe(iii)/DQ2, Al(iii)/DQ716, and Al(iii)/DQ2 solution chemistry was investigated in aqueous 0.6 mol kg(-1) (Na)Cl at 25 degrees C by means of potentiometric titrations, UV-vis spectrophotometry, and (1)H-NMR spectroscopy. DQ716 exhibited the highest coordination efficiency towards Fe(iii) and Al(iii) among all hydroxypyridinecarboxylic acids examined so far, whereas DQ2 complexes were significantly less stable. These results were confirmed by chelation efficiency measurements performed in an octanol-aqueous solution in the presence of those ligands and metals. Partitioning experiments at pH 7.4 showed both DQ716 and DQ2, and their Fe(iii) and Al(iii) complexes, to be hydrophilic. According to the voltammetric data, the free ligands (DQ716 and DQ2) and their metal complexes are not predicted to undergo redox cycling at in vivo conditions. The standard reduction potentials of these complexes, and the kinetics of their formation and dissociation, were obtained. The toxicity of DQ716 and of DQ2 was investigated with human cancer cell lines and normal human fibroblasts. Cytotoxic effects were observed only for DQ2 at 0.1 mM, following 3 d exposure. According to our results, DQ716 has the required favourable properties to be a chelating agent for Fe and Al.
In view of a possible application to Fe and Al chelation therapy, 2-methyl-3-hydroxy-4-pyridinecarboxylic acid (DT2) was synthesised, and its complex formation, electrochemical and cytotoxic ...properties were studied. The complexing properties of DT2 towards Fe(III) and Al(III) were investigated in aqueous 0.6 m (Na)Cl at 25 degrees C by means of potentiometric titrations, UV-vis spectrophotometry, and 1H NMR spectroscopy. DT2 is a triprotic acid (H3L+) having pKa1 = 0.47, pKa2 = 5.64 and pKa3 = 11.18. The metal-ligand complexes observed in solution and their corresponding stability constants (log beta values) are the following: FeLH (19.38), FeL (16.01), FeLH(-1) (12.28), FeL2H2 (37.29), FeL3H3 (53.41), FeL3H2 (47.99), FeL3H (41.21) and FeL3 (34.1); AlLH (17.43), AlL2H2 (33.74), AlL2H (27.6), AlL3H3 (48.72), AlL3H2 (42.67), AlL3H (35.8) and AlL3 (27.92). The complex formation between DT2 and Fe(II) was studied by UV-vis: the weak complex FeLH (log beta = 15.8) was detected. DT2 shows a lower complexation efficiency with Fe(III) and Al(III) than that of other available chelators, but higher than that of its non-methylated analogue 3-hydroxy-4-pyridinecarboxylic acid (DT0). The electrochemical behaviour of DT2 was investigated by means of cyclic voltammetry, indicating that the oxidation of the ligand proceeds through a two electron process with a CECE mechanism. Voltammetric curves suggest that the oxidation or the reduction of DT2 in vivo is unlikely. According to the thermodynamic data, also the Fe(III)-DT2 complexes do not undergo redox cycling at physiological pH. Amperometric titrations of solutions containing Fe(III) and DT2 at pH = 5 indicated the same Fe(III) : ligand stoichiometric ratio as calculated from potentiometric data. The toxicity of DT2 and of other simple hydroxypyridinecarboxylic acids was investigated in vitro and no cytotoxic activity was observed (IC50 > 0.1 mM) on cancer cell lines and also on primary human cells, following a three day exposure.
Voltammetric experiments were used to demonstrate the possibility to rapidly obtain stability constants, E degrees values and kinetic parameters of Fe(III) complexes with ...1,6-dimethyl-4-hydroxy-3-pyridinecarboxylic acid (DQ716) at pH 2.3 and 4-hydroxy-2-methyl-3-pyridinecarboxylic acid (DQ2) at pH 3. Fe(III) diffusion coefficient (D(Fe)= 5.5.10(-6) cm(2)/s), heterogeneous electron transfer kinetic constant (k degrees = 2.7.10(-4)cm/s), symmetry coefficient (alpha= 0.57) and Fe(III)/Fe(II) standard reduction potential (E degrees = 0.53 V vs. SCE) were determined beforehand and used to obtain all the other results. Digital simulation together with potentiometric data were used to define the whole reaction system in terms of thermodynamic and kinetic parameters. In particular, E degrees and the dissociation kinetic constant, k(b), of the 1:1 (E degrees = 0.22 V vs. SCE, k(b)= 0.032 s(-1)), 1:2 (E degrees = 0.098 V vs. SCE; k(b)= 0.22 s(-1)) and 1:3 (E degrees < or =-0.29 V vs. SCE, k(b)= 157.9 s(-1)) Fe(III)/DQ716 complexes, were estimated. Stability constants of the Fe(II) complexes were computed from these values. The voltammetric data were also interpreted with two independent formalisms: (1) solution of an equation system and (2) a curve fitting method based on the Koutecky-Levich equation. Both approaches allowed us to obtain the speciation of a Fe(III)/DQ716 solution at pH 2.3. Moreover, the second approach allowed the evaluation of the kinetic contributions, the stepwise stability constant of Fe(III)L(2) (7.65 +/- 0.07), and to define the mathematical formalization of the experimental result which link some key-points of the voltammetric curve (inflection points and plateaux) to D(Fe), k degrees , alpha(j) and E degrees . This approach was also successfully applied to obtain the speciation of a Fe(III)/DQ2 solution at pH 3.
Commercially, polyamide 12 (PA12) is one of the polymers applied as an internal insulation layer in offshore exploitation. The present study aims to produce a hybrid system based on PA12 with 5 wt% ...of a nanoclay grade (montmorillonite – MMT) and evaluate its effect on the barrier behavior of the PA12 matrix, the exact grade used in the pressure layer of flexible pipe, over carbon steel AISI 1020, metallic alloy responsible for providing the mechanical properties to flexible pipes. The barrier behavior, related to ion and molecule diffusion in synthetic production water, was assessed by Electrochemical Impedance Spectroscopy (EIS) and linear sweep voltammetry (LSV) analysis, which allow for interpreting the carbon steel corrosion mechanisms. One also carried out Fourier transform infrared, X‐ray diffraction, and Scanning electron microscopy analyzes. The data showed that the MMT lamellae are well‐dispersed in the PA12 matrix. EIS and LSV analysis results showed higher corrosion protection efficiency by the system composed of PA12/MMT once compared to the system without adding the load.
The superimposed clinical features of motor neuron disease (MND) and frontotemporal lobar degeneration (FTLD) comprise a rare neurological overlap syndrome that represents a diagnostic challenge to ...neurologists. Currently, FTLD‐MND is considered a distinct entity and its clinicopathological basis has recently been reviewed. Our aim is to present a patient with MND and non‐fluent rapidly progressive aphasia with clinical, imaging and histopathological correlation, as well as a brief review of the literature. We demonstrated the selective corticospinal tract (CST) and temporal lobe involvement using T1 spin‐echo with an additional magnetization transfer contrast pulse on resonance (T1 SE/MTC) and FLAIR MR sequences in our patient, with further clinical and histopathological correlation. To the best of our knowledge, there is no description about the use of these particular MR sequences in the evaluation of FTLD‐MND patients.
In recent decades, there has been an increase in the number of publications related to the hypersurfaces of real space forms with two principal curvatures. The works focus mainly on the case when one ...of the two principal curvatures is simple. The purpose of this paper is to study a slightly more general class of complete minimal hypersurfaces in real space forms of constant curvature
c
, namely those with
n
-
1
principal curvatures having the same sign everywhere. From assumptions on the scalar curvature
R
and the Gauss–Kronecker curvature
K
we characterize Clifford tori if
c
>
0
and prove that
K
is identically zero if
c
≤
0
.