Lability of heavy metal species in aquatic humic substances characterized by ion exchange with cellulose phosphate

Labile metal species in aquatic humic substances (HSs) were characterized by ion exchange on cellulose phosphate (CellPhos) by applying an optimized batch procedure. The HSs investigated were pre-extracted from humic-rich waters by ultrafiltration and a resin XAD 8 procedure. The HS-metal species studied were formed by complexation with Cd(II), Ni(II), Cu(II), Mn(II) and Pb(II) as a function of time and the ratio ions to HSs. The kinetics and reaction order of this exchange process were studied. At the beginning (<3 min), the labile metal fractions are separated relatively quickly. After 3 min, the separation of the metal ions proceeds with uniform half-lives of about 12-14 min, revealing rather slow first-order kinetics. The metal exchange between HSs and CellPhos exhibited the following order of metal lability with the studied HSs: Cu > Pb > Mn > Ni > Cd. The required metal determinations were carried out by atomic absorption spectrometry.

Electron impact and chemical ionization mass spectral analyses of methyl esters species of free mycolic acid fraction from Rhodococcus lentifragmentus

The free mycolic acid fraction from Rhodococcus lentifragmentus was derivatized to methyl esters and further fractionated into saturated (F-0), monounsaturated (F-1) and diunsaturated (F-2) species using argentation-TLC. Methyl esters fractions F-0, F-1 and F-2, accounting for approximately 7.4%, 53.1% and 39.5%, respectively, were analyzed by electron impact (EI) and chemical ionization (CI) mass spectrometries. According to EI-MS, peaks observed for M(+)-18, that were prominent compared to those representing M(+)-32 and M(+)-(18 + 32), indicated that the carbon chain size ranged from C-36 to C-48. The pyrolytic cleavage of methyl mycolates (R(2)-CHOH-CH(R(1))-COOCH3), following the McLafferty rearrangement released fragment ions corresponding to, (a) the alpha-subunit, representing the fatty acid methyl ester (R(1)-CH2-COOCH3), methyl hexadecanoate, methyl tetradecanoate and methyl dodecanoate in decreasing order of relative intensity of peaks, and (b) the beta-subunit, representing the meroaldehyde moiety (R(2)-CHO). The saturated meroaldehyde species exhibited peaks representing meroaldehyde minus 18 mass units in which R(2) ranged from C19H39 to C31H63. The monunsaturated species exhibited peaks representing the meroaldehyde in which R(2) ranged from C19H37 to C31H61; peaks corresponding to meroaldehyde minus 18 mass units appeared only in the most abundant components, C29H57CHO, C27H53CHO, C25H49CHO and C31H61CHO, in a decreasing order of relative abundance. The diunsaturated species exhibited peaks essentially corresponding to meroaldehyde in which R(2) corresponded to C31H59 and C29H55; the latter displayed a relative intensity that was about one-half compared to that of the former. Fractions F-0, F-1 and F-2 showed a more intense pyrolytic fragmentation under CI-MS in contrast to results found under EI-MS. Therefore, peaks representing the alpha-subunit and the beta-subunit were more prominent than the ones representing the fragmentation of the hydrocarbon chain. Moreover, the beta-subunit of saturated species exhibited peaks corresponding to meroaldehyde plus hydrogen, and no dehydration of the beta-subunit occurred in this case. In turn, the beta-subunit of monounsaturated and diunsaturated species showed peaks representing both the meroaldehyde plus hydrogen and its dehydration product plus hydrogen. Thus, the presence of unsaturation in the meroaldehyde subunit of methyl mycolate facilitates appearance of dehydration fragment ions under chemical ionization procedure.

Development and Evaluation of a Nanoporous Iron (Hydr)oxide Electrode for Phosphate Sensing

Nanoporous iron (hydr) oxide electrodes are evaluated as phosphate sensors using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The intensity of the reduction peak current (I-cp) of the ferrihydrite working electrode is tied to phosphate concentration at low pH; however, a hematite electrode combined with the use of EIS provided reliable sensing data at multiple pH values. Nanoporous hematite working electrodes produced an impedance phase component (theta) that shifts with increasing phosphate, and, at chosen frequencies, theta values were fitted for the range 1 nM to 0.1 mM phosphate at pH 4 and pH 7 in 5 mM NaClO4.

Discovery of novel Trypanosoma cruzi glyceraldehyde-3-phosphate dehydrogenase inhibitors

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Paper-based diffusive gradients in thin films technique coupled to energy dispersive X-ray fluorescence spectrometry for the determination of labile Mn, Co, Ni, Cu, Zn and Pb in river water

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

Synergistic action of both Aspergillus niger and Burkholderia cepacea in co-culture increases phosphate solubilization in growth medium

Co-inoculation of the fungus Aspergillus niger and the bacterium Burkholderia cepacia was undertaken to understand the interaction between different species of phosphate-solubilizing microorganisms (PSM). PSM were inoculated in a single or mixed (A. nigerB.similar to cepacia) culture. During 9 similar to days of incubation, microbial biomass was enhanced, accompanied with increases in the levels of soluble phosphate and titratable acidity, as well as increased acid phosphatase activity. Production of acids and levels of phosphate solubilization were greater in the co-culture of A.similar to nigerB.similar to cepacia than in the single culture. The quantity of phosphate solubilized by the co-culture ranged from 40.51 +/- 0.60 to 1103.64 +/- 1.21 similar to mu g similar to PO4 3-similar to mL-1 and was 922% higher than single cultures. pH of the medium dropped from 7.0 to 3.0 in the A.similar to niger culture, 3.1 in the co-culture, and 4.2 in the B.similar to cepacia culture. on the third day of postinoculation, acid production by the co-culture (mean 5.40 +/- 0.31 similar to mg NaOH mL-1) was 1990% greater than single cultures. Glucose concentration decreased almost completely (9799% of the starting concentration) by the ninth day of the incubation. These results show remarkable synergism by the co-culture in comparison with single cultures in the solubility of CaHPO4 under in vitro conditions. This synergy between microorganisms can be used in poor available phosphate soils to enhance phosphate solubilization.

Supersensitivity of the isolated guinea-pig vas deferens induced by a toxic fraction of scorpion venom (Tityus serrulatus)

1. Tityustoxin (TsTx), a toxic fraction of Tityus serrulatus venom, was studied on the isolated guinea-pig vas deferens. It increased significantly the maximal response of the preparation to both norepinephrine and acetylcholine and decreased the effective median dose of norepinephrine. 2. The effect of TsTx on norepinephrine median dose was unchanged when atropinized or pharmacologically 'denervated' preparations were used but was abolished when both procedures were associated. 3. Atropinization of pharmacologically denervated muscles almost never modify the TsTx-induced increase in the maximal response to norepinephrine. 4. On denervated or phentolamine-treated muscles TsTx-induced increase in the maximal response to acetylcholine was abolished. 5. It was concluded that toxin predominantly induces adrenergic postsynaptic supersensitivity. 6. Of minor significance, it also induces presynaptic cholinergic and adrenergic supersensitivity. 7. Comparison of these results with those of crude venom indicates that TsTx effects may result from the sum of the effects of subcomponents not demonstrated by the chemical procedures here utilized.

Soluble phosphate accumulation by Aspergillus niger from fluorapatite

In order to determine conditions that may provide greater solubilization of insouluble phosphate, the fungus Aspergillus niger was grown in a stationary culture containing modified citrate medium supplemented with 800 mg fluorapatite per litre. Solubilization of insouluble phosphate increased with fungal growth, reaching a maximum after 11 days of culture. Soluble phosphate levels were correlated with pH of the culture medium but not with titratable acidity values, probably due to the metabolic activity of the fungus resulting from consumption of sugar in the culture medium. Fructose, glucose, xylose, and sucrose were the carbohydrates that favoured fluorapatite solubilization the most when compared with galactose and maltose. Although increasing fructose concentrations in the culture medium favoured mycelial growth, increased total acidity and a fall in pH, soluble phosphate levels were reduced, probably owing to consumption by the rapidly growing fungus. Among the nitrogen sources tested, ammonium salts favoured the production of larger amounts of soluble phosphate than organic nitrogen (peptone or urea) or nitrate, corresponding to the lowest pH and highest titratable acidity values obtained. © 1988 Springer-Verlag.

Isoniazid acetylating phenotype in patients with paracoccidioidomycosis and its relationship with serum sulfadoxin levels, glucose-6-phosphate dehydrogenase and glutathione reductase activities

The authors evaluated the isoniazid acetylating phenotype and measured hematocrit, hemoglobin, glucose-6-phosphate dehydrogenase and glutathione reductase activities plus serum sulfadoxin levels in 39 patients with paracoccidioidomycosis (33 males and 6 females) aged 17 to 58 years. Twenty one (53.84%) of the patients presented a slow acetylating phenotype and 18 (46.16%) a fast acetylating phenotype. Glucose-6-phosphate-dehydrogenase (G6PD) activity was decreased in 5(23.80%) slow acetylators and in 4 (22.22%) fast acetylators. Glutathione reductase activity was decreased in 14 (66.66%) slow acetylators and in 12(66.66%) fast acetylators. Serum levels of free and total sulfadoxin were higher in slow acetylator (p _ 0.02). Analysis of the results permitted us to conclude that serum sulfadoxin levels are related to the acetylator phenotype. Furthermore, sulfadoxin levels were always above 50 μg/ml, a value considered therapeutic. Glutathione reductase deficiency observed in 66% of patients may be related to the intestinal malabsorption of nutrients, among them riboflavin, a FAD precursor vitamin, in patients with paracoceidioidomycosis.

Structure and catalytic mechanism of glucosamine 6-phosphate deaminase from Escherichia coli at 2.1 Å resolution

Background: Glucosamine 6-phosphate deaminase from Escherichia coli is an allosteric hexameric enzyme which catalyzes the reversible conversion of D-glucosamine 6-phosphate into D-fructose 6-phosphate and ammonium ion and is activated by N-acetyl-D-glucosamine 6-phosphate. Mechanistically, it belongs to the group of aldose-ketose isomerases, but its reaction also accomplishes a simultaneous amination/deamination. The determination of the structure of this protein provides fundamental knowledge for understanding its mode of action and the nature of allosteric conformational changes that regulate its function. Results: The crystal structure of glucosamine 6-phosphate deaminase with bound phosphate ions is presented at 2.1 Å resolution together with the refined structures of the enzyme in complexes with its allosteric activator and with a competitive inhibitor. The protein fold can be described as a modified NAD-binding domain. Conclusions: From the similarities between the three presented structures, it is concluded that these represent the enzymatically active R state conformer. A mechanism for the deaminase reaction is proposed. It comprises steps to open the pyranose ring of the substrate and a sequence of general base-catalyzed reactions to bring about isomerization and deamination, with Asp72 playing a key role as a proton exchanger.

Factors determining rock phosphate solubilization by microorganisms isolated from soil

Forty two soil isolates (31 bacteria and 11 fungi) were studied for their ability to solubilize rock phosphate and calcium phosphate in culture medium. Eight bacteria and 8 fungi possessed solubilizing ability. Pseudomonas cepacia and Penicillium purpurogenum showed the highest activity. There was a correlation between final pH value and titratable acidity (r = - 0.29 to -0.87) and between titratable acidity and soluble phosphate (r = 0.22 to 0.99). Correlation values were functions of insoluble phosphate and of the group of microorganisms considered. A high correlation was observed between final pH and soluble phosphate only for the rock phosphates inoculated with the highest concentration of solubilizing bacteria (r = -0.73 to -0.98).

Preconcentration of heavy metals ions from aqueous solutions by means of cellulose phosphate: An application in water analysis

Cellulose phosphate (CELLPHOS) was studied as a collector for analytical preconcentration of traces of Cd(II), Cr(III), Cu(II) and Ni(II) from aqueous sample solution. It has been proved that using chromatographic columns packed with CELLPHOS for preconcentration and 1.0 mol 1 -1 HCl for elution the adsorbed analytes are quantitatively enriched. An enrichment factor of 20 (100 ml sample, 5 ml concentrate) was achieved by this separation procedure, which was applied to a series of water analyses (river, sea, bog water).