Plant availability of trace elements in sewage sludge-treated soils: methodology¹

Synthetic root exudates were formulated based on the organic acid composition of root exudates derived from the rhizosphere of aseptically grown corn plants, pH of the rhizosphere, and the background chemical matrices of the soil solutions. The synthetic root exudates, which mimic the chemical conditions of the rhizosphere environment where soil-borne metals are dissolved and absorbed by plants, were used to extract metals from sewage-sludge treated soils 16 successive times. The concentrations of Zn, Cd, Ni, Cr, and Cu of the sludge-treated soil were 71.74, 0.21, 15.90, 58.12, and 37.44 mg kg-1, respectively. The composition of synthetic root exudates consisted of acetic, butyric, glutaric, lactic, maleic, propionic, pyruvic, succinic, tartaric, and valeric acids. The organic acid mixtures had concentrations of 0.05 and 0.1 mol L-1 -COOH. The trace elements removed by successive extractions may be considered representative for the availability of these metals to plants in these soils. The chemical speciation of the metals in the liquid phase was calculated; results showed that metals in sludge-treated soils were dissolved and formed soluble complexes with the different organic acid-based root exudates. The most reactive organic acid ligands were lactate, maleate, tartarate, and acetate. The inorganic ligands of chloride and sulfate played insignificant roles in metal dissolution. Except for Cd, free ions did not represent an important chemical species of the metals in the soil rhizosphere. As different metals formed soluble complexes with different ligands in the rhizosphere, no extractor, based on a single reagent would be able to recover all of the potentially plant-available metals from soils; the root exudate-derived organic acid mixtures tested in this study may be better suited to recover potentially plant-available metals from soils than the conventional extractors.

Organic acids in the rhizosphere and phytoavailability of sewage sludge-borne trace elements

The aim of this work was to quantify low molecular weight organic acids in the rhizosphere of plants grown in a sewage sludge-treated media, and to assess the correlation between the release of the acids and the concentrations of trace-elements in the shoots of the plants. The species utilized in the experiment were cultivated in sand and sewage sludge-treated sand. The acetic, citric, lactic, and oxalic acids, were identified and quantified by high performance liquid chromatography in samples collected from a hydroponics system. Averages obtained from each treatment, concentration of trace elements in shoots and concentration of organic acids in the rhizosphere, were compared by Tukey test, at 5% of probability. Linear correlation analysis was applied to verify an association between the concentrations of organic acids and of trace elements. The average composition of organic acids for all plants was: 43.2, 31.1, 20.4 and 5.3% for acetic, citric, lactic, and oxalic acids, respectively. All organic acids evaluated, except for the citric acid, showed a close statistical agreement with the concentrations of Cd, Cu, Ni, and Zn found in the shoots. There is a positive relationship between organic acids present in the rhizosphere and trace element phytoavailability.

Determination of chemical elements in africanized Apis mellifera (Hymenoptera: Apidae) honey samples from the State of Piauí, Brazil

Honey is a food used since the most remote times, appreciated for its characteristic flavor, considerable nutritional value and medicinal properties; however, little information exists about the presence of chemical elements in it. The objectives of this work were to determine the chemical elements present in 38 honey samples, collected directly from beekeepers from the State of Piauí, Brazil and to verify whether they presented any contamination. The chemical elements were determined by means of Total Reflection X-ray Fluorescence. The means of three replicates were: K (109.671 ± 17.487), Ca (14.471 ± 3.8797), Ti (0.112 ± 0.07), Cr (0.196 ± 0.11), Mn (0.493 ± 0.103), Fe (1.722 ± 0.446), Co (0.038), Ni (0.728 ± 0.706), Cu (0.179 ± 0.0471), Zn (0.967 ± 0.653), Se (not detected), Br (not detected), Rb (0.371 ± 0.097), Sr (0.145 ± 0.45), Ba (11.681), Hg (not detected), and Pb (0.863) µg g-1.

The use of Rich and Suter diagrams to explain the electron configurations of transition elements

Rich and Suter diagrams are a very useful tool to explain the electron configurations of all transition elements, and in particular, the s¹ and s0 configurations of the elements Cr, Cu, Nb, Mo, Ru, Rh, Pd, Ag, and Pt. The application of these diagrams to the inner transition elements also explains the electron configurations of lanthanoids and actinoids, except for Ce, Pa, U, Np, and Cm, whose electron configurations are indeed very special because they are a mixture of several configurations.

Spectroscopic analysis of C80 doping with group III and group V elements using semiempirical PM3 molecular modelling technique

Semiempirical calculations at the level of PM3 of theory were carried out to study the structural and electronic properties of C80 and some of its doped derivatives with the elements of group III and V at the level of PM3 of theory. We have selected these elements to be substituted in the fullerene-C80 cage in order to show the effect of such structural change on the electronic properties of the molecules studied. The theoretical IR spectra, some of physical and chemical properties of the molecules studied are obtained and discussed.

Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.

Numerical evaluation of the modulus of longitudinal elasticity in structural round timber elements of the Eucalyptus genus

Currently, the standards that deal with the determination of the properties of rigidity and strength for structural round timber elements do not take in consideration in their calculations and mathematical models the influence of the existing irregularities in the geometry of these elements. This study has as objective to determine the effective value of the modulus of longitudinal elasticity for structural round timber pieces of the Eucalyptus citriodora genus by a technique of optimization allied to the Inverse Analysis Method, to the Finite Element Method and the Least Square Method.

Genetic and antigenic analysis of Babesia bigemina isolates from five geographical regions of Brazil

A molecular epidemiological study was performed with Babesia bigemina isolates from five geographical regions of Brazil. The genetic analysis was done with random amplification of polymorphic DNA (RAPD), repetitive extragenic palindromic elements-polymerase chain reaction (REP-PCR) and enterobacterial repetitive intergenic consensus sequences-polymerase chain reaction (ERIC-PCR) that showed genetic polymorphism between these isolates and generated fingerprinting. In RAPD, ILO872 and ILO876 primers were able to detect at least one fingerprinting for each B. bigemina isolate. The amplification of B. bigemina DNA fragments by REP-PCR and ERIC-PCR gave evidence for the presence in this haemoprotozoan of the sequences described previously in microorganisms of the bacterial kingdom. For the first time it was demonstrated that both techniques can be used for genetic analysis of a protozoan parasite, although the ERIC-PCR was more discriminatory than REP-PCR. The dendogram with similarity coefficient among isolates showed two clusters and one subcluster. The Northeastern and Mid-Western isolates showed the greatest genetic diversity, while the Southeastern and Southern isolates were the closest. The antigenic analysis was done through indirect fluorescent antibody technique and Western blotting using a panel of monoclonal antibodies directed against epitopes on the merozoite membrane surface, rhoptries and membrane of infected erythrocytes. As expected, the merozoite variable surface antigens, major surface antigen (MSA)-1 and MSA-2 showed antigenic diversity. However, B cell epitopes on rhoptries and infected erythrocytes were conserved among all isolates studied. In this study it was possible to identify variable and conserved antigens, which had already been described as potential immunogens. Considering that an attenuated Babesia clone used as immunogen selected populations capable of evading the immunity induced by this vaccine, it is necessary to evaluate more deeply the cross-protection conferred by genetically more distant Brazilian B. bigemina isolates and make an evaluation of the polymorphism degree of variable antigens such as MSA-1 and MSA-2.

Geometric nonlinear dynamic analysis of plates and shells using eight-node hexahedral finite elements with reduced integration

This work presents a geometric nonlinear dynamic analysis of plates and shells using eight-node hexahedral isoparametric elements. The main features of the present formulation are: (a) the element matrices are obtained using reduced integrations with hourglass control; (b) an explicit Taylor-Galerkin scheme is used to carry out the dynamic analysis, solving the corresponding equations of motion in terms of velocity components; (c) the Truesdell stress rate tensor is used; (d) the vector processor facilities existing in modern supercomputers were used. The results obtained are comparable with previous solutions in terms of accuracy and computational performance.

In vitro radioautographic studies of the biodistribution of radiopharmaceuticals on blood elements

In the present study we evaluated the binding of the radiopharmaceuticals sodium pertechnetate (Na 99mTcO4), methylenediphosphonic acid (99mTc-MDP) and glucoheptonate acid (99mTc-GHA) to blood elements using centrifugation and radioautographic techniques. Heparinized blood was incubated with the labelled compounds for 0, 1, 2, 3, 4, 6 and 24 h. Plasma (P) and blood cells (BC) were isolated and precipitated with 5% trichloroacetic acid (TCA), and soluble (SF) and insoluble fractions (IF) were separated. Blood samples were prepared (0 and 24 h) and coated with LM-1 radioautographic emulsions and percent radioactivity (%rad) in P and BC was determined. The binding of Na 99mTcO4 (%rad) to P was 61.2% (0 h) and 46.0% (24 h), and radioautography showed 63.7% (0 h) and 43.3% (24 h). The binding to BC was 38.8% (0 h) and 54.0% (24 h), and radioautography showed 36.3% (0 h) and 56.7% (24 h). 99mTc-MDP study presented 91.1% (0 h) to P and 87.2% (24 h), and radioautography showed 67.9% (0 h) and 67.4% (24 h). The binding to BC was 8.9% (0 h) and 12.8% (24 h), and radioautography showed 32.1% (0 h) and 32.6% (24 h). 99mTc-GHA study was 90.1% (0 h) to P and 79.9% (24 h), and radioautography showed 67.2% (0 h) and 60.1% (24 h). The binding to BC was 9.9% (0 h) and 20.1% (24 h), and radioautography showed 32.8% (0 h) and 39.9% (24 h). The comparison of the obtained results suggests that the binding to plasma and blood cells in the two techniques used (radioautography and centrifugation) is qualitatively in accordance

Protection of plasmid DNA by a Ginkgo biloba extract from the effects of stannous chloride and the action on the labeling of blood elements with technetium-99m

Ginkgo biloba extract (EGb) is a phytotherapeutic agent used for the treatment of ischemic and neurological disorders. Because the action of this important extract is not fully known, assays using different biological systems need to be performed. Red blood cells (RBC) are labeled with technetium-99m (Tc-99m) and used in nuclear medicine. The labeling depends on a reducing agent, usually stannous chloride (SnCl2). We assessed the effect of different concentrations of EGb on the labeling of blood constituents with Tc-99m, as sodium pertechnetate (3.7 MBq), and on the mobility of a plasmid DNA treated with SnCl2 (1.2 µg/ml) at room temperature. Blood was incubated with EGb before the addition of SnCl2 and Tc-99m. Plasma (P) and RBC were separated and precipitated with trichloroacetic acid, and soluble (SF-P and SF-RBC) and insoluble (IF-P and IF-RBC) fractions were isolated. The plasmid was incubated with Egb, SnCl2 or EGb plus SnCl2 and agarose gel electrophoresis was performed. The gel was stained with ethidium bromide and the DNA bands were visualized by fluorescence in an ultraviolet transilluminator system. EGb decreased the labeling of RBC, IF-P and IF-RBC. The supercoiled form of the plasmid was modified by treatment with SnCl2 and protected by 40 mg/ml EGb. The effect of EGb on the tested systems may be due to its chelating action with the stannous ions and/or pertechnetate or to the capability to generate reactive oxygen species that could oxidize the stannous ion.

Essential regulatory elements for NHE3 gene transcription in renal proximal tubule cells

The objectives of the present study were to identify the cis-elements of the promoter absolutely required for the efficient rat NHE3 gene transcription and to locate positive and negative regulatory elements in the 5’-flanking sequence (5’FS), which might modulate the gene expression in proximal tubules, and to compare this result to those reported for intestinal cell lines. We analyzed the promoter activity of different 5’FS segments of the rat NHE3 gene, in the OKP renal proximal tubule cell line by measuring the activity of the reporter gene luciferase. Because the segment spanning the first 157 bp of 5’FS was the most active it was studied in more detail by sequential deletions, point mutations, and gel shift assays. The essential elements for gene transcription are in the region -85 to -33, where we can identify consensual binding sites for Sp1 and EGR-1, which are relevant to NHE3 gene basal transcription. Although a low level of transcription is still possible when the first 25 bp of the 5’FS are used as promoter, efficient transcription only occurs with 44 bp of 5’FS. There are negative regulatory elements in the segments spanning -1196 to -889 and -467 to -152, and positive enhancers between -889 and -479 bp of 5’FS. Transcription factors in the OKP cell nuclear extract efficiently bound to DNA elements of rat NHE3 promoter as demonstrated by gel shift assays, suggesting a high level of similarity between transcription factors of both species, including Sp1 and EGR-1.

Transcranial direct current stimulation and repetitive transcranial magnetic stimulation in consultation-liaison psychiatry

Patients with clinical diseases often present psychiatric conditions whose pharmacological treatment is hampered due to hazardous interactions with the clinical treatment and/or disease. This is particularly relevant for major depressive disorder, the most common psychiatric disorder in the general hospital. In this context, nonpharmacological interventions could be useful therapies; and, among those, noninvasive brain stimulation (NIBS) might be an interesting option. The main methods of NIBS are repetitive transcranial magnetic stimulation (rTMS), which was recently approved as a nonresearch treatment for some psychiatric conditions, and transcranial direct current stimulation (tDCS), a technique that is currently limited to research scenarios but has shown promising results. Therefore, our aim was to review the main medical conditions associated with high depression rates, the main obstacles for depression treatment, and whether these therapies could be a useful intervention for such conditions. We found that depression is an important and prevalent comorbidity in a variety of diseases such as epilepsy, stroke, Parkinson's disease, myocardial infarction, cancer, and in other conditions such as pregnancy and in patients without enteral access. We found that treatment of depression is often suboptimal within the above contexts and that rTMS and tDCS therapies have been insufficiently appraised. We discuss whether rTMS and tDCS could have a significant impact in treating depression that develops within a clinical context, considering its unique characteristics such as the absence of pharmacological interactions, the use of a nonenteral route, and as an augmentation therapy for antidepressants.

Bilateral repetitive transcranial magnetic stimulation for treatment-resistant depression: a systematic review and meta-analysis of randomized controlled trials

There has been concern regarding the use of controversial paradigms for repetitive transcranial magnetic stimulation (rTMS) to manage treatment-resistant depression (TRD). This meta-analysis assessed the efficacy of bilateral rTMS compared with unilateral and sham rTMS in patients with TRD. PubMed, Embase, CENTRAL, PsycINFO, Web of Science, EAGLE and NTIS databases were searched to identify relevant studies, and randomized controlled trials (RCTs) on bilateral rTMS for TRD patients were included. The response was defined as the primary outcome, and remission was the secondary outcome. Ten RCTs that included 634 patients met the eligibility criteria. The risk ratio (RRs) of both the primary and secondary outcomes of bilateral rTMS showed non-significant increases compared to unilateral rTMS (RR=1.01, P=0.93; odds ratio [OR]=0.77, P=0.22). Notably, the RR of the primary bilateral rTMS outcome was significantly increased compared to that for sham rTMS (RR=3.43, P=0.0004). The results of our analysis demonstrated that bilateral rTMS was significantly more effective than sham rTMS but not unilateral rTMS in patients with TRD. Thus, bilateral rTMS may not be a useful paradigm for patients with TRD.