RESUMO

The decline in the quality of water resources in the Amazon is very rapid in cities suffering from unplanned urban growth. The region has two defined seasons, winter (wet) and summer (dry), which directly affect the behavior of contaminants in aquatic ecosystems. The aim of this study was to assess the ecological and human health risks associated with the use of the watershed. In addition, an ecological index was proposed: the Quality Index for Aquatic Life, for the risk of contaminants to aquatic life. Sampling was carried out at six points in the Juá watershed. Physicochemical parameters, major anions, metals and total phosphorus were analyzed at both stations between 2020 and 2021. The highest concentrations of contaminants were found in the rainy season, due to the washing away of the banks. In this sense, Cl presented a concentration more than 307 times higher than that permitted by Brazilian legislation (wet). The ecological index showed that the watershed has a high risk of metals such as Cr III and Cr VI for the biota. The human health risk analysis showed a low risk; however, the lack of basic sanitation in the city indicates that monitoring of urban water resources is necessary.

Assuntos

Metais Pesados , Poluentes Químicos da Água , Humanos , Qualidade da Água , Monitoramento Ambiental , Ecossistema , Poluentes Químicos da Água/análise , Medição de Risco , Metais Pesados/análise , Rios , China

RESUMO

In this work, the influence of oxyanions on the catalytic reduction of nitrates using formic acid as the reducing agent was studied as well as the influence of bicarbonate, sulfate, and phosphate co-anions on the catalytic nitrate reduction with Pd:In/Al2O3 (1:0.25 wt.%). A negative effect on nitrate conversion was observed in the following order: phosphate > sulfate > bicarbonate, showing a strong influence of electrostatic adsorption on the catalytic reduction of nitrate. However, no direct trend was observed relating the levels of interferents to the impact on the selectivity of the bimetallic catalyst using formic acid as a reducing agent. For both bicarbonate and phosphate, at lower levels, higher selectivity to nitrogen was obtained than for the reaction in the absence of interferents. On the other hand, increasing sulfate concentration led to a decrease in nitrate conversion. The mixtures of co-anions also showed a decrease in the catalytic activity. At 120 min, a N2 selectivity higher than 95% was obtained, except for the C50-S20 (bicarbonate 50 ppm-sulfate 20 ppm) mixture which showed the lowest selectivity to N2 value (87.3%). The loss of catalyst activity was found to be reversible and not permanent.

Assuntos

Nitratos , Água , Substâncias Redutoras , Bicarbonatos , Sulfatos , Catálise

RESUMO

The photodetachment and stability of R-Mandelate, the deprotonated form of the R-Mandelic acid, was investigated by observing the neutral species issued from either simple photodetachment or dissociative photodetachment in a cold anions set-up. R-Mandalate has the possibility to form an intramolecular ionic hydrogen-bond between adjacent hydroxyl and carboxylate groups. The potential energy surface along the proton transfer (PT) coordinate between both groups (O- …H+ …- OCO) features a single local minima, with the proton localized on the O- group (OH…- OCO). However, the structure with the proton localized on the - OCO group (O- …HOCO) is also observed because it falls within the extremity of the vibrational wavefunction of the OH…- OCO isomer along the PT coordinate. The stability of the corresponding radicals, produced upon photodetachment, is strongly dependent on the position of the proton in the anion: the radicals produced from the OH…- OCO isomer decarboxylate without barrier, while the radicals produced from the O- …HOCO isomer are stable.

Assuntos

Hidrogênio , Prótons , Isomerismo , Ácidos Mandélicos , Ânions/química

RESUMO

Aluminyl anions are low-valent, anionic, and carbenoid aluminum species commonly found stabilized with potassium cations from the reaction of Al-halogen precursors and alkali compounds. These systems are very reactive toward the activation of σ-bonds and in reactions with electrophiles. Various research groups have detected that the potassium atoms play a stabilization role via electrostatic and cation ⋯ π interactions with nearby (aromatic)-carbocyclic rings from both the ligand and from the reaction with unsaturated substrates. Since stabilizing K⋯H bonds are witnessed in the activation of this class of molecules, we aim to unveil the role of these metals in the activation of the smaller and less polarizable H2 molecule, together with a comprehensive characterization of the reaction mechanism. In this work, the activation of H2 utilizing a NON-xanthene-Al dimer, [K{Al(NON)}]2 (D) and monomeric, [Al(NON)]- (M) complexes are studied using density functional theory and high-level coupled-cluster theory to reveal the potential role of K+ atoms during the activation of this gas. Furthermore, we aim to reveal whether D is more reactive than M (or vice versa), or if complicity between the two monomer units exits within the D complex toward the activation of H2 . The results suggest that activation energies using the dimeric and monomeric complexes were found to be very close (around 33 kcal mol-1 ). However, a partition of activation energies unveiled that the nature of the energy barriers for the monomeric and dimeric complexes are inherently different. The former is dominated by a more substantial distortion of the reactants (and increased interaction energies between them). Interestingly, during the oxidative addition, the distortion of the Al complex is minimal, while H2 distorts the most, usually over 0.77 Δ E d i s t ≠ . Overall, it is found here that electrostatic and induction energies between the complexes and H2 are the main stabilizing components up to the respective transition states. The results suggest that the K+ atoms act as stabilizers of the dimeric structure, and their cooperative role on the reaction mechanism may be negligible, acting as mere spectators in the activation of H2 . Cooperation between the two monomers in D is lacking, and therefore the subsequent activation of H2 is wholly disengaged.

RESUMO

This paper presents the Outer Plug Standardization - OPS, a novel technique as an alternative for the classic internal standardization using multiple injection in capillary zone electrophoresis is proposed herein. This technique was applied in a new method for the determination of chloride, nitrate and sulfate in rainwater samples. After the injection accuracy was tested and proved to be a minor error source (average 1.26% RSD), the OPS was applied and it improved the intra-day and inter-day precision of the analytical method by 32.5% and 24.7%, respectively. Using a capillary with effective length of 23.5 cm the electrophoretic separation of the three inorganic anions could be achieved in <1 min, with detection limits of 0.05, 0.09 and 0.11 mg L-1 for chloride, nitrate and sulfate, respectively. Also, the statistical t-test was applied to the results obtained for 82 rainwater samples that were collected and analyzed applying both the method developed in this study and the official APHA 4140 method where no statistical difference was noted within a 95% confidence level.

Assuntos

Cloretos , Projetos de Pesquisa , Ânions , Calibragem , Padrões de Referência

RESUMO

Excessive UV solar radiation exposure causes human health risks; therefore, the study of multifunctional filters is important to skin UV protective ability and also to other beneficial activities to the human organism, such as reduction of reactive oxygen species (ROS) responsible for cellular damages. Potential multifunctional filters were obtained by intercalating of ferulate anions into layered simple metal hydroxides (LSH) through anion exchange and precipitation at constant pH methods. Ultrasound treatment was used in order to investigate the structural changes in LSH-ferulate materials. Structural and spectroscopic analyses show the formation of layered materials composed by a mixture of LSH intercalated with ferulate anions, where carboxylate groups of ferulate species interact with LSH layers. UV-VIS absorption spectra and in vitro SPF measurements indicate that LSH-ferulate systems have UV shielding capacity, mainly UVB protection. The results of reactive species assays show the ability of layered compounds in capture DPPH•, ABTS•+, ROO•, and HOCl/OCl- reactive species. LSH-ferulate materials exhibit antioxidant activity and singular optical properties that enable their use as multifunctional filters.

Assuntos

Hidróxidos/química , Protetores contra Radiação/química , Raios Ultravioleta/efeitos adversos , Zinco/química , Ânions/química , Antioxidantes/efeitos da radiação , Humanos , Substâncias Intercalantes/química , Metais/química , Espécies Reativas de Oxigênio/química , Pele/efeitos dos fármacos , Pele/efeitos da radiação , Sistema Solar/química , Análise Espectral

RESUMO

Erythropoietin (EPO) is a cytokine originally used for its effects on the hematopoietic system, and is widely prescribed around the world. In the present study, the effects of EPO administration on p-aminohippurate (PAH, a prototype organic anion) pharmacokinetics and on the renal expression of PAH transporters were evaluated. Male Wistar rats were treated with EPO or saline (control group). After 42 h, PAH was administered, and plasma samples were obtained at different time points to determine PAH levels. PAH levels in renal tissue and urine were also assessed. The renal expression of PAH transporters was evaluated by Western blotting. EPO-treated rats showed an increase in PAH systemic clearance, in its elimination rate constant, and in urinary PAH levels, while PAH in renal tissue was decreased. Moreover, EPO administration increased the expression of the transporters of the organic anions evaluated. The EPO-induced increase in PAH clearance is accounted for by the increase in its renal secretion mediated by the organic anion transporters. The goal of this study is to add important information to the wide knowledge gap that exists regarding drug-drug interactions. Owing to the global use of EPO, these results are useful in terms of translation into clinical practice.

Assuntos

Ânions/farmacocinética , Eritropoetina/farmacologia , Rim/efeitos dos fármacos , Rim/metabolismo , Animais , Masculino , Ratos , Ratos Wistar

RESUMO

Due to their potential binding sites, barbituric acid (BA) and its derivatives have been used in metal coordination chemistry. Yet their abilities to recognize anions remain unexplored. In this work, we were able to identify four structural features of barbiturates that are responsible for a certain anion affinity. The set of coordination interactions can be finely tuned with covalent decorations at the methylene group. DFT-D computations at the BLYP-D3(BJ)/aug-cc-pVDZ level of theory show that the C-H bond is as effective as the N-H bond to coordinate chloride. An analysis of the electron charge density at the C-H⋅⋅⋅Cl- and N-H⋅⋅⋅Cl- bond critical points elucidates their similarities in covalent character. Our results reveal that the special acidity of the C-H bond shows up when the methylene group moves out of the ring plane and it is mainly governed by the orbital interaction energy. The amide and carboxyl groups are the best choices to coordinate the ion when they act together with the C-H bond. We finally show how can we use this information to rationally improve the recognition capability of a small cage-like complex that is able to coordinate NaCl.

RESUMO

In this study we evaluated the effects of the prepartum anionic diet on the electrolyte balance and calcemia of high producing dairy cows in the first days of lactation, and investigated the impact on the frequency of subclinical hypocalcemia (SCH). Sixty healthy Holstein cows, producing 30 kg of milk/day, handled in intensive system (compost barn), were distributed in groups (n=15) according to lactation order: first, second, third, and fourth to sixth. In the last three weeks before calving they received a diet with negative DCAD (-6mEq/100g DM) and high chloride content. After calving, they received a diet with positive DCAD (18mEq/100g DM). Urine pH was measured before calving. Serum Na+, Cl-, K+, and total Ca concentrations, and the strong ion difference (SID3) were determined in samples taken soon after calving (0h), 24, 48, 72 and 96h after. The frequencies of SCH were determined considering the critical value of 2.125mmol/L (8.5mg/dL). Two-way repeated measures ANOVA and chi-square test were used for comparisons. The cows eliminated acidic urine before calving. Na+, K+, Cl-, and SID3 values did not differ between groups. Na+ and K+ did not vary between days; Cl- was elevated at calving and decreased until 72h; and SID3 was reduced at calving and increased up to 48h. The Ca levels were reduced until 24h and increased up to 72h. Cows of third and fourth to sixth lactations presented lower values up to 24h. SCH was observed in almost half of the cows (43.3% to 55%) until 48h. The maintenance of hypocalcemia for three or more consecutive days occurred in 53.3% of third and fourth to sixth lactations cows. Ingestion of a high chloride prepartum anionic diet led to hyperchloremic acidosis and this imbalance was reversed on the second postpartum day. The induced effects on electrolyte and acid-base balances were not able to prevent the occurrence of SCH in the first days of lactation.(AU)

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Os objetivos do estudo foram avaliar os efeitos que a dieta aniônica pré-parto provoca sobre o equilíbrio eletrolítico e sobre a calcemia de vacas leiteiras de alta produção nos primeiros dias de lactação, e verificar o impacto sobre a frequência da hipocalcemia subclínica (HSC). Sessenta fêmeas hígidas HPB, com produção de 30 kg de leite/dia, manejadas em sistema intensivo (compost barn), foram distribuídas por grupos (n=15) de acordo com a ordem de lactação: primeira, segunda, terceira e quarta a sexta. Nas três semanas pré-parto receberam dieta com DCAD negativa (-6mEq/100g MS) e teor de cloreto elevado. Após o parto receberam dieta com DCAD positiva (18mEq/100g MS). O pH da urina foi mensurado antes do parto. As concentrações séricas de Na+, Cl-, K+ e Ca total e a diferença de íons fortes (SID3) foram determinadas em amostras colhidas ao parto (0h), 24, 48, 72 e 96h após. As frequências de HSC foram determinadas considerando-se o valor crítico de 2,125mmol/L (8,5mg/dL). ANOVA de medidas repetidas e teste de qui-quadrado foram empregados para as comparações. As vacas eliminavam urina ácida antes do parto. Os valores de Na+, K+, Cl- e SID3 não diferiram entre os grupos. Na+ e K+ não variaram entre os dias; Cl- era elevado ao parto e diminuiu até 72h; e SID3 era reduzida ao parto e aumentou até 48h. A calcemia era reduzida até 24h e se elevou até 72h. Vacas de terceira e de quarta a sexta lactações apresentaram valores mais baixos até 24h. A HSC foi observada em quase metade das vacas (43,3% a 55%) até 48h. A manutenção de hipocalcemia por três ou mais dias seguidos ocorreu em 53,3% das vacas de terceira e de quarta a sexta lactações. A ingestão de dieta aniônica pré-parto com alto teor de cloreto provocou acidose hiperclorêmica e este desequilíbrio se reverteu no segundo dia pós-parto. Os efeitos induzidos sobre os equilíbrios eletrolítico e ácido base não foram capazes de prevenir a ocorrência de HSC nos primeiros dias da lactação.(AU)

Assuntos

Animais , Feminino , Gravidez , Bovinos , Acidose/induzido quimicamente , Dieta/veterinária , Hipocalcemia/prevenção & controle , Equilíbrio Hidroeletrolítico , Cloreto de Amônio

RESUMO

In this study we evaluated the effects of the prepartum anionic diet on the electrolyte balance and calcemia of high producing dairy cows in the first days of lactation, and investigated the impact on the frequency of subclinical hypocalcemia (SCH). Sixty healthy Holstein cows, producing 30 kg of milk/day, handled in intensive system (compost barn), were distributed in groups (n=15) according to lactation order: first, second, third, and fourth to sixth. In the last three weeks before calving they received a diet with negative DCAD (-6mEq/100g DM) and high chloride content. After calving, they received a diet with positive DCAD (18mEq/100g DM). Urine pH was measured before calving. Serum Na+, Cl-, K+, and total Ca concentrations, and the strong ion difference (SID3) were determined in samples taken soon after calving (0h), 24, 48, 72 and 96h after. The frequencies of SCH were determined considering the critical value of 2.125mmol/L (8.5mg/dL). Two-way repeated measures ANOVA and chi-square test were used for comparisons. The cows eliminated acidic urine before calving. Na+, K+, Cl-, and SID3 values did not differ between groups. Na+ and K+ did not vary between days; Cl- was elevated at calving and decreased until 72h; and SID3 was reduced at calving and increased up to 48h. The Ca levels were reduced until 24h and increased up to 72h. Cows of third and fourth to sixth lactations presented lower values up to 24h. SCH was observed in almost half of the cows (43.3% to 55%) until 48h. The maintenance of hypocalcemia for three or more consecutive days occurred in 53.3% of third and fourth to sixth lactations cows. Ingestion of a high chloride prepartum anionic diet led to hyperchloremic acidosis and this imbalance was reversed on the second postpartum day. The induced effects on electrolyte and acid-base balances were not able to prevent the occurrence of SCH in the first days of lactation.(AU)

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Os objetivos do estudo foram avaliar os efeitos que a dieta aniônica pré-parto provoca sobre o equilíbrio eletrolítico e sobre a calcemia de vacas leiteiras de alta produção nos primeiros dias de lactação, e verificar o impacto sobre a frequência da hipocalcemia subclínica (HSC). Sessenta fêmeas hígidas HPB, com produção de 30 kg de leite/dia, manejadas em sistema intensivo (compost barn), foram distribuídas por grupos (n=15) de acordo com a ordem de lactação: primeira, segunda, terceira e quarta a sexta. Nas três semanas pré-parto receberam dieta com DCAD negativa (-6mEq/100g MS) e teor de cloreto elevado. Após o parto receberam dieta com DCAD positiva (18mEq/100g MS). O pH da urina foi mensurado antes do parto. As concentrações séricas de Na+, Cl-, K+ e Ca total e a diferença de íons fortes (SID3) foram determinadas em amostras colhidas ao parto (0h), 24, 48, 72 e 96h após. As frequências de HSC foram determinadas considerando-se o valor crítico de 2,125mmol/L (8,5mg/dL). ANOVA de medidas repetidas e teste de qui-quadrado foram empregados para as comparações. As vacas eliminavam urina ácida antes do parto. Os valores de Na+, K+, Cl- e SID3 não diferiram entre os grupos. Na+ e K+ não variaram entre os dias; Cl- era elevado ao parto e diminuiu até 72h; e SID3 era reduzida ao parto e aumentou até 48h. A calcemia era reduzida até 24h e se elevou até 72h. Vacas de terceira e de quarta a sexta lactações apresentaram valores mais baixos até 24h. A HSC foi observada em quase metade das vacas (43,3% a 55%) até 48h. A manutenção de hipocalcemia por três ou mais dias seguidos ocorreu em 53,3% das vacas de terceira e de quarta a sexta lactações. A ingestão de dieta aniônica pré-parto com alto teor de cloreto provocou acidose hiperclorêmica e este desequilíbrio se reverteu no segundo dia pós-parto. Os efeitos induzidos sobre os equilíbrios eletrolítico e ácido base não foram capazes de prevenir a ocorrência de HSC nos primeiros dias da lactação.(AU)

Assuntos

Animais , Feminino , Gravidez , Bovinos , Acidose/induzido quimicamente , Dieta/veterinária , Hipocalcemia/prevenção & controle , Equilíbrio Hidroeletrolítico , Cloreto de Amônio

RESUMO

The influence of common groundwater major ions on arsenic (As) retention by native limestones was studied through column experiments. Columns were packed with rock particles (0.5-1.41 mm) and fed with solutions containing As, and chloride (Cl), sulfate, bicarbonate or fluoride (F) in concentrations similar to those measured in one of the most As-rich wells of Mexico. Besides, other solutions were also treated containing multiples or submultiples of those anion concentrations. Physico-chemical parameters, As, and each anion concentrations were determined weekly along 4 months. After the end of the experiments rocks collected from the top of the columns were analyzed by XRF, XRD, and SEM-WDS. Concentrations of As decreased from 1.2 mg/L to values below the Mexican drinking water standard (0.025 mg/L), since the first week in the solutions containing F or Cl keeping low values afterwards, indicating that they do not interfere with As removal. However, although As strongly decreased in the solutions containing sulfate since the first week, it started to increase from the 12th week in the highest concentrated solution. Bicarbonate was the anion affecting most As retention, since, after its decrease below 0.025 mg/L in the 2nd week for both solutions (30 mg/L and 300 mg/L), it started to increase since the 7th week in the most concentrated one, but maintained a low concentration in the least concentrated solution. Saturation index calculations and XRD analyses did not evidence the formation of As minerals. However, SEM elemental maps and XRF analyses showed the presence of As on the rocks after the treatments. Results indicate that As may be retained by sorption. Sulfate and bicarbonate compete with As for sorption sites. Results showed that native limestones are an option for treating As polluted water. Experiments also indicated that bicarbonate and sulfate may interfere with As removal depending on their concentrations.

RESUMO

Phosphorus (P) is a nutrient for plant growth but also a pollutant in water bodies causing eutrophication. The source of P is mainly human and animal wastewater and runoffs from different land uses. The objective of the present study is to evaluate P removal and recovery processes by ion exchange (IE) with solid carbonate (SC) in biodigestor-treated swine effluent (BTSE) using hydrogeochemical modeling. For this, BTSE compositions were obtained by literature review. A synthetized and characterized SC was used and the ion exchange site concentration ([SC-IE]) and the IE constants (Kie) were obtained experimentally and applied to model P and major anion removal and recovery processes. P recovery was evaluated for different BTSE compositions and several concentrations of SC, dissolved P (HPO42-), competing anions such as SO42-, and CO32-. The simulations suggest that a [SC-IE]:[HPO4] of 1.4 molar ratio would allow the recovery of 90% of HPO4 in BTSE, and at average alkalinity concentrations in BTSE, CO32- would compete with HPO4 for the SC-IE. The P recovery by the SC-IE process was compared with two other methods commonly used in P removal from BTSE: removal with aluminum sulfate and precipitation of struvite as a function of pH. The results suggest that SC-IE is the most efficient method in the pH range of BTSE. Besides, HPO42- was readily recovered as inorganic P that may be reused in agriculture and industrial processes.

Assuntos

Carbonatos , Fósforo , Animais , Troca Iônica , Fosfatos , Estruvita , Suínos , Eliminação de Resíduos Líquidos , Águas Residuárias

RESUMO

The effects of four inorganic anions (Cl-, SO42-, HCO3-, NO3-) usually present in groundwater were investigated on the photo-Fenton degradation of 2,4-dichlorophenoxyacetic acid (2,4-D). A kinetic model derived from a reaction sequence is proposed using the ferrioxalate complex as iron source at pH close to natural conditions (pH = 5). It was demonstrated that oxalate not only maintained iron in solution for the natural groundwater system, but also increased the photochemical activation of the process. Results showed that the minimum conversion of 2,4-D for the simulated groundwater after 180 min was 63.80%. This value was only 14.1% lower than the conversion achieved without anions. However, with all anions together, the consumption of hydrogen peroxide (HP) per mole of herbicide showed an increase with respect to the test without anions. Only one kinetic parameter was estimated for each anion applying a nonlinear regression method. Subsequently, these optimized kinetic constants were used to simulate the system behaviour, considering the influence of all the studied anions together. A good agreement between kinetic model predictions and experimental data was observed, with the following errors: RMSE2,4-D = 3.98 × 10-3 mM, RMSEHP = 1.83 × 10-1 mM, RMSEOX = 1.39 × 10-2 mM, and RMSE2,4-DCP = 5.59 × 10-3  mM.

RESUMO

Alarming amounts of organic pollutants are being detected in waterbodies due to their ineffective removal by conventional treatment techniques, which warn of the urgent need of developing new technologies for their remediation. In this context, advanced oxidation processes (AOPs), especially those based on Fenton reactions, have proved to be suitable alternatives, due to their efficacy of removing persistent organic compounds. However, the use of ferrous iron in these processes has several operational constraints; to avoid this, an alternative iron source was here investigated: zero-valent-iron (ZVI). A Fenton-like process based on the activation of a recently explored oxidant-persulfate (PS)-with ZVI was applied to degrade an emerging contaminant: Amicarbazone (AMZ). The influence of ZVI size and source, PS/ZVI ratio, pH, UVA radiation, dissolved O2, and inorganic ions was evaluated in terms of AMZ removal efficiency. So far, this is the first time these parameters are simultaneously investigated, in the same study, to evaluate a ZVI-activated PS process. The radical mechanism was also explored and two radical scavengers were used to determine the identity of major active species taking part in the degradation of AMZ. The degradation efficiency was found to be strongly affected by the ZVI dosage, while positively affected by the PS concentration. The PS/ZVI system enabled AMZ degradation in a wide range of pH, although with a lower efficiency under slightly alkaline conditions. Dissolved O2 revealed to play an important role in reaction kinetics as well as the presence of inorganic ions. UVA radiation seems to improve the degradation kinetics only in the presence of extra O2 content. Radicals quenching experiments indicated that both sulfate (SO4•-) and hydroxyl (•OH) radicals contributed to the overall oxidation performance, but SO4•- was the dominant oxidative species.

Assuntos

Ferro/química , Sulfatos/química , Triazóis/isolamento & purificação , Poluentes Químicos da Água/isolamento & purificação , Purificação da Água/métodos , Concentração de Íons de Hidrogênio , Radical Hidroxila/química , Cinética , Oxirredução , Triazóis/química , Poluentes Químicos da Água/química

RESUMO

A new quinoline-amide calix[4]arene 3-receptor for detection of hazardous anions and cations have been synthesized. The 3-receptor was examined for its sensing properties towards several different anions (Cr2O72-, SCN-, F-, Cl-, NO3-) and metal ions (Hg2+, Cd2+, Ag+) by UV-vis and fluorescence spectroscopies. It was detected that the 3-receptor has only sensing ability for Cr2O72- and Hg2+ ions, resulting in the association constants higher for Cr2O72- than to the Hg2+ ions. High selectivity towards Cr2O72- were also observed by fluorescence measurement among other ions (F-, Cl-, SCN-, Hg2+, Cd2+, Ag+) with a low limit of detection (7.36×10-6moldm-3). Proton NMR anion-binding investigations revealed a strong interaction of Cr2O72- anion with NH and CH groups of the receptor, showing that the combination with hydrogen-bonds donor groups strengthened the anion receptor association. Furthermore, remarkable association constants for dichromate anion obtained by all techniques strongly suggest the 3-receptor as a selective Cr(VI) sensor.

RESUMO

Paracetamol is an active ingredient commonly found in pharmaceutical formulations in combination with one of the following compounds: codeine, orphenadrine, promethazine, scopolamine, and tramadol. In this work, we propose a unique analytical method for determination of these active ingredients in pharmaceutical samples. The method is based on capillary electrophoresis with capacitively coupled contactless conductivity detection. The separation was achieved on a fused silica capillary (50 cm total length, 40 cm effective length, and 50 µm id) using an optimized background electrolyte composed of 20 mmol/L ß-alanine/4 mmol/L sodium chloride/4 µmol/L sodium hydroxide (pH 9.6). Each sample can be analyzed in a single run (≤2 min) and the limits of detection were 2.5, 0.62, 0.63, 2.5, 15, and 1.6 µmol/L for scopolamine, tramadol, orphenadrine, promethazine, codeine, and paracetamol, respectively. Recovery values for spiked samples were between 94 and 104%.

Assuntos

Acetaminofen/análise , Eletroforese Capilar , Codeína/análise , Composição de Medicamentos , Orfenadrina/análise , Prometazina/análise , Escopolamina/análise , Tramadol/análise

RESUMO

AIM: To examine renal expression of organic anion transporter 5 (Oat5) and sodium-dicarboxylate cotransporter 1 (NaDC1), and excretion of citrate in rats with acute extrahepatic cholestasis. METHODS: Obstructive jaundice was induced in rats by double ligation and division of the common bile duct (BDL group). Controls underwent sham operation that consisted of exposure, but not ligation, of the common bile duct (Sham group). Studies were performed 21 h after surgery. During this period, animals were maintained in metabolic cages in order to collect urine. The urinary volume was determined by gravimetry. The day of the experiment, blood samples were withdrawn and used to measure total and direct bilirubin as indicative parameters of hepatic function. Serum and urine samples were used for biochemical determinations. Immunoblotting for Oat5 and NaDC1 were performed in renal homogenates and brush border membranes from Sham and BDL rats. Immunohistochemistry studies were performed in kidneys from both experimental groups. Total RNA was extracted from rat renal tissue in order to perform reverse transcription polymerase chain reaction. Another set of experimental animals were used to evaluate medullar renal blood flow (mRBF) using fluorescent microspheres. RESULTS: Total and direct bilirubin levels were significantly higher in BDL animals, attesting to the adequacy of biliary obstruction. An important increase in mRBF was determined in BDL group (Sham: 0.53 ± 0.12 mL/min per 100 g body weight vs BDL: 1.58 ± 0.24 mL/min per 100 g body weight, P < 0.05). An increase in the urinary volume was observed in BDL animals. An important decrease in urinary levels of citrate was seen in BDL group. Besides, a decrease in urinary citrate excretion (Sham: 0.53 ± 0.11 g/g creatinine vs BDL: 0.07 ± 0.02 g/g creatinine, P < 0.05) and an increase in urinary excretion of H(+) (Sham: 0.082 ± 0.03 µmol/g creatinine vs BDL: 0.21 ± 0.04 µmol/g creatinine, P < 0.05) were observed in BDL animals. We found upregulations of both proteins Oat5 and NaDC1 in brush border membranes where they are functional. Immunohistochemistry technique corroborated these results for both proteins. No modifications were observed in Oat5 mRNA and in NaDC1 mRNA levels in kidney from BDL group as compared with Sham ones. CONCLUSION: Citrate excretion is decreased in BDL rats, at least in part, because of the higher NaDC1 expression. Using the outward gradient of citrate generated by NaDC1, Oat5 can reabsorb/eliminate different organic anions of pathophysiological importance.

Assuntos

Colestase Extra-Hepática/metabolismo , Transportadores de Ácidos Dicarboxílicos/metabolismo , Icterícia Obstrutiva/metabolismo , Rim/metabolismo , Transportadores de Ânions Orgânicos Dependentes de Sódio/metabolismo , Simportadores/metabolismo , Animais , Bilirrubina/sangue , Biomarcadores/sangue , Biomarcadores/urina , Colestase Extra-Hepática/sangue , Colestase Extra-Hepática/genética , Colestase Extra-Hepática/urina , Ácido Cítrico/urina , Ducto Colédoco/cirurgia , Transportadores de Ácidos Dicarboxílicos/genética , Modelos Animais de Doenças , Icterícia Obstrutiva/sangue , Icterícia Obstrutiva/genética , Icterícia Obstrutiva/urina , Ligadura , Masculino , Transportadores de Ânions Orgânicos Dependentes de Sódio/genética , Ratos Wistar , Circulação Renal , Eliminação Renal , Simportadores/genética , Fatores de Tempo , Regulação para Cima

RESUMO

TRK transporters, a class of proteins which generally carry out the bulk of K(+) accumulation in plants, fungi, and bacteria, mediate ion currents driven by the large membrane voltages (-150 to -250 mV) common to non-animal cells. Bacterial TRK proteins resemble K(+) channels in their primary sequence, crystallize as membrane dimers having intramolecular K(+)-channel-like folding, and complex with a cytoplasmic collar formed of four RCK domains (Nature 471:336, 2011; Ibid 496:324, 2013). Fungal TRK proteins appear simpler in form than the bacterial members, but do possess two special features: a large built-in regulatory domain, and a highly conserved pair of transmembrane helices (TM7 and TM8, ahead of the C-terminus), which were postulated to facilitate intramembranal oligomerization (Biophys. J. 77:789, 1999; FEMS Yeast Res. 9:278, 2009). A surprising associated functional process in the fungal proteins which have been explored (Saccharomyces, Candida, and Neurospora) is facilitation of channel-like chloride efflux. That process is suppressed by osmoprotective agents, appears to involve hydrophobic gating, and strongly resembles conduction by Cys-loop ligand-gated anion channels. And it leads to a rather general hypothesis: that the thermodynamic tendency for hydrophobic or amphipathic transmembrane helices to self-organize into oligomers can create novel ionic pathways through biological membranes: fundamental hydrophobic nanopores, pathways of low selectivity governed by the chaotropic behavior of individual ionic species and under the strong influence of membrane voltage.

Assuntos

Cloretos/metabolismo , Canais de Potássio/metabolismo , Proteínas de Saccharomyces cerevisiae/metabolismo , Sequência de Aminoácidos , Dados de Sequência Molecular , Potássio/metabolismo , Canais de Potássio/química , Estrutura Terciária de Proteína , Proteínas de Saccharomyces cerevisiae/química , Leveduras/genética , Leveduras/metabolismo

RESUMO

The purpose of the work is to compare the influence of the multilamellarity, phase state, lipid head groups and ionic media on the origin of the surface potential of lipid membranes. With this aim, we present a new analysis of the zeta potential of multilamellar and unilamellar vesicles composed by phosphatidylcholines (PC) and phosphatidylethanolamines (PE) dispersed in water and ionic solutions of polarizable anions, at temperatures below and above the phase transition. In general, the adsorption of anions seems to explain the origin of the zeta potential in vesicles only above the transition temperature (Tc). In this case, the sign of the surface potential is ascribed to a partial orientation of head group moiety toward the aqueous phase. This is noticeable in PC head groups but not in PEs, due to the strong lateral interaction between PO and NH group in PE.

Assuntos

1,2-Dipalmitoilfosfatidilcolina/química , Dimiristoilfosfatidilcolina/química , Bicamadas Lipídicas/química , Fosfatidiletanolaminas/química , Ânions/química , Condutividade Elétrica , Modelos Químicos , Modelos Moleculares , Conformação Molecular , Tamanho da Partícula , Eletricidade Estática , Temperatura , Lipossomas Unilamelares/química

RESUMO

Objective. Evaluate the acid-base balance (ABB) in bovines with diarrheic backgrounds in four areas of Montería, Colombia. Materials and methods. From a total of 300 pregnant cows, 60 were selected with their newborns. A direct inspection was performed of vital signs on the calves and the ABB indicators were determined using a gasometric method. Data were processed by means of descriptive statistics and the Duncan test was used to differentiate between the averages. The degree of association was established between the ABB indicators in cows and calves by using the Pearson correlation and a comparison of proportions was performed on the indexes of the newborns. Results. Regarding the cows, the ABB indicators were found within the reference values; however, in the calves the pH, pCO2, HCO3-, the anion gap (AG) and the bases excess (BE) varied. A correlation was found between AG, BE and metabolic hydrogen ions (M*H). The AG in cows and calves showed notable differences (p<0.05) among the farms in the study. According to the numeric classification system, the suction reflect indicated a greater percentage of calves in group one. Conclusions. The ABB analyte measurement in cows was similar to the consulted reference; however, in calves some analytes did not coincide. This suggests metabolic acidosis in newborn calves due to the increase of AG and the decrease of BE. Additionally, its correlation with M*H opens the possibility of new proposals to determine ABB in bovines.

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Objetivo. Evaluar el equilibrio ácido-básico (EAB) en bovinos con antecedentes diarreicos de cuatro zonas de Montería, Colombia. Materiales y métodos. De un total de 300 vacas preñadas se seleccionaron 60 vacas y sus recién nacidos. Se realizó una inspección directa de los signos vitales en terneros y los indicadores del EAB se determinaron mediante técnica gasométrica. Los datos se procesaron mediante estadística descriptiva y para la diferencia entre medias se empleó la prueba de Duncan. El grado de asociación se estableció entre los indicadores del EAB en vacas y terneros mediante la correlación de Pearson y una comparación de proporciones se realizó en los índices del recién nacido. Resultados. En las vacas, los indicadores del EAB se encontraron dentro de los valores de referencia; sin embargo, en los terneros varió el pH, pCO2, HCO3-, la brecha aniónica (AG) y el exceso de bases (EB). Se encontró correlación entre AG, EB e hidrogeniones metabólicos (H+M). El AG en vacas y terneros indicó diferencias notables (p<0.05) entre las fincas de estudio. De acuerdo con el sistema de calificación numérica, el signo reflejo de succión indicó el mayor porcentaje de terneros en el grupo uno. Conclusiones. La medición de los analitos del EAB en vacas fue similar a la referencia consultada; sin embargo, en terneros no coincidió con algunos analitos. Se sugiere acidosis metabólica en los terneros recién nacidos por el aumento del AG y descenso del EB, además, su correlación con los H+M abre la posibilidad de nuevas propuestas para la determinación del EAB en bovinos.