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Colorectal cancer (CRC) is the third leading cause of cancer deaths in the world. Standard drugs currently used for the treatment of advanced CRC-such as 5-fluorouracil (5FU)-remain unsatisfactory in their results due to their high toxicity, high resistance, and adverse effects. In recent years, mitochondria have become an attractive target for cancer therapy due to higher transmembrane mitochondrial potential. We synthesized gallic acid derivatives linked to a ten-carbon aliphatic chain associated with triphenylphosphonium (TPP+C10), a lipophilic cationic molecule that induces the uncoupling of the electron transport chain (ETC). Other derivatives, such as gentisic acid (GA-TPP+C10), have the same effects on colorectal cancer cells. Although part of our group had previously reported preparing these structures by a convergent synthesis route, including their application via flow chemistry, there was no precedent for a new methodology for preparing these compounds. In this scenario, this study aims to develop a new linear synthesis strategy involving an essential step of Steglich esterification under mild conditions (open flask) and a high degree of reproducibility. Moreover, the study seeks to associate GA-TPP+C10 with 5FU to evaluate synergistic antineoplastic effects. In addition, we assess the antimigratory effect of GA-TPP+C10 and TPP+C10 using human and mouse metastatic CRC cell lines. The results show a new and efficient synthesis route of these compounds, having synergistic effects in combination with 5FU, increasing apoptosis and enhancing cytotoxic properties. Additionally, the results show a robust antimigratory effect of GATPP+C10 and TPP+C10, reducing the activation pathways linked to tumor progression and reducing the expression of VEGF and MMP-2 and MMP-9, common biomarkers of advanced CRC. Moreover, TPP+C10 and GA-TPP+C10 increase the activity of metabolic signaling pathways through AMPK activation. The data allow us to conclude that these compounds can be used for in vivo evaluations and are a promising alternative associated with conventional therapies for advanced colorectal cancer. Additionally, the reported intermediates of the new synthesis route could give rise to analog compounds with improved therapeutic activity.
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The influence of metal ions on the structure of amyloid- ß (Aß) protofibril models was studied through molecular dynamics to explore the molecular mechanisms underlying metal-induced Aß aggregation relevant in Alzheimer's disease (AD). The models included 36-, 48-, and 188-mers of the Aß42 sequence and two disease-modifying variants. Primary structural effects were observed at the N-terminal domain, as it became susceptible to the presence of cations. Specially when ß-sheets predominate, this motif orients N-terminal acidic residues toward one single face of the ß-sheet, resulting in the formation of an acidic region that attracts cations from the media and promotes the folding of the N-terminal region, with implications in amyloid aggregation. The molecular phenotype of the protofibril models based on Aß variants shows that the AD-causative D7N mutation promotes the formation of N-terminal ß-sheets and accumulates more Zn2+, in contrast to the non-amyloidogenic rodent sequence that hinders the ß-sheets and is more selective for Na+ over Zn2+ cations. It is proposed that forming an acidic ß-sheet domain and accumulating cations is a plausible molecular mechanism connecting the elevated affinity and concentration of metals in Aß fibrils to their high content of ß-sheet structure at the N-terminal sequence.
Assuntos
Peptídeos beta-Amiloides , Simulação de Dinâmica Molecular , Peptídeos beta-Amiloides/química , Peptídeos beta-Amiloides/metabolismo , Peptídeos beta-Amiloides/genética , Conformação Proteica em Folha beta , Humanos , Zinco/metabolismo , Zinco/química , Doença de Alzheimer/metabolismo , Fragmentos de Peptídeos/química , Fragmentos de Peptídeos/metabolismo , Fragmentos de Peptídeos/genética , Metais/metabolismo , Metais/químicaRESUMO
The dynamics and responses to mulching management processes, which affect sustainability in tropical agroecosystems, remain poorly understood. Therefore, this study aims to evaluate and distinguish the short-and long-term effects of mulch of leguminous biomass on fertility of a tropical soil enriched with calcium. This experiment was conducted using the treatments: Long-term mulching (LTM) consisted of planting without mulch in 2019 in soil that had been mulched for six years previously, while short-term mulching (STM) consisted of planting without mulch for six years and with mulch only in 2019. LTM + STM consisted of planting in mulched soil for seven years (from 2013 to 2019), while LTM + synthetic nitrogen (LTM + sN) consisted of the LTM treatment with the addition of 150 kg N ha-1. The remaining treatments were STM + sN; LTM + STM + sN; bare soil with sN, and bare soil without sN as control. In areas with LTM the interactions between products derived from biomass, sN, and Ca resulted in higher total SOC and BS, while STM maintained soil moisture, decreased penetration resistance, and enhanced N uptake providing biological nitrogen able to replace sN for maize nutrition. The positive effects of short- and long-term mulching were cumulative as they increased accumulated N by maize in 163%, and maize grain yield by 125% (4.77-10.78 Mg ha-1) compared to cultivation with sN without mulch. Our results showed that interactions between continuos mulch of leguminous biomass, Ca and sN prevent degradation of agricultural land in Amazonian conditions. Therefore, this combination must be recommended to prevent Amazonian soil management, which in turn reduces the risk of new deforestation in Amazonian periphery.
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Theobroma cacao agro-industrial waste (WTC) has been characterized and tested as an effective biosorbent to remove Cd(II) from aqueous media. At the optimum pH of 5.0, a maximum adsorption capacity of qe,max = 58.5 mg g-1 was determined. The structural and morphological characterization have been conducted by FTIR, SEM/EDX, and TGA measurements. The SEM/EDX results confirmed that the metals are adsorbed on the surface. C-O-C, OH, CH, NH, and C=O functional groups were identified by FTIR. TGA results were consistent with the presence of hemicellulose. Biosorption kinetics were rapid during the first 30 min and then reached equilibrium. The corresponding experimental data were well fitted to pseudo-first and -second order models, the latter being the best. The biosorption isotherm data were also well fitted to Temkin, Langmuir, and Freundlich models, showing that several sorption mechanisms may be involved in the Cd(II) biosorption process, which was characterized as exothermic (ΔH0 < 0), feasible, and spontaneous (ΔG0 < 0). In binary (Cd-Pb and Cd-Cu) and ternary (Cd-Pb-Cu) systems, Cu(II) and particularly Pb(II) co-cations exert strong antagonistic effects. Using HNO3, effective good regeneration of WTC was obtained to efficiently remove Cd(II) up to three times.
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Herein, we describe the synthesis, crystal structure, and electronic properties of {[K2(dmso)(H2O)5][Ni2(H2mpba)3]·dmso·2H2O}n (1) and [Ni(H2O)6][Ni2(H2mpba)3]·3CH3OH·4H2O (2) [dmso = dimethyl sulfoxide; CH3OH = methanol; and H4mpba = 1,3-phenylenebis(oxamic acid)] bearing the [Ni2(H2mpba)3]2- helicate, hereafter referred to as {NiII2}. SHAPE software calculations indicate that the coordination geometry of all the NiII atoms in 1 and 2 is a distorted octahedron (Oh) whereas the coordination environments for K1 and K2 atoms in 1 are Snub disphenoid J84 (D2d) and distorted octahedron (Oh), respectively. The {NiII2} helicate in 1 is connected by K+ counter cations yielding a 2D coordination network with sql topology. In contrast to 1, the electroneutrality of the triple-stranded [Ni2(H2mpba)3] 2- dinuclear motif in 2 is achieved by a [Ni(H2O)6]2+ complex cation, where the three neighboring {NiII2} units interact in a supramolecular fashion through four R22(10) homosynthons yielding a 2D array. Voltammetric measurements reveal that both compounds are redox active (with the NiII/NiI pair being mediated by OH- ions) but with differences in formal potentials that reflect changes in the energy levels of molecular orbitals. The NiII ions from the helicate and the counter-ion (complex cation) in 2 can be reversibly reduced, resulting in the highest faradaic current intensities. The redox reactions in 1 also occur in an alkaline medium but at higher formal potentials. The connection of the helicate with the K+ counter cation has an impact on the energy levels of the molecular orbitals; this experimental behavior was further supported by X-ray absorption near-edge spectroscopy (XANES) experiments and computational calculations.
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This work investigated the synthesis and characterization of alginate/starch porous materials and their application as copper ions adsorbents from aqueous media. Initially, pregel aqueous solutions with different biopolymer concentrations (1, 3, and 5% w/w) and alginate contents (25, 50, and 75% w/w) were prepared. Hydrogel formation was performed by internal and external gelation methods. Finally, the drying step was done via CO2sc leading to aerogels and via freeze-drying leading to cryogels. Process parameters influence on the final properties of materials was evaluated by BET isotherms, SEM, EDS, and TGA. Regardless the gelation method applied, interesting materials with meso- and macro-pore structure were prepared from pregel mixtures with 3% w/w biopolymer concentration and an alginate content of only 25% w/w. Low alginate content reduces the final cost of the materials. Concerning copper removal, the adsorption data were well fitted to the pseudo-second order kinetic model for aerogels and cryogels, showing aerogels the highest adsorption capacity (40 mg/g) and removal efficiency (â¼ 92%). Materials demonstrated excellent reusability throughout five consecutive adsorption/desorption cycles. Hence, environmentally friendly materials with a high practical value as low-cost bioadsorbents were synthesized, having great performance in the removal of copper ions from aqueous solution.
Assuntos
Alginatos , Cobre , Poluentes Químicos da Água , Adsorção , Alginatos/química , Cobre/química , Criogéis/química , Amido , Água/química , Poluentes Químicos da Água/químicaRESUMO
BACKGROUND: Parasitic human infectious diseases are a worldwide health problem due to the increased resistance to conventional drugs. For this reason, the identification of novel molecular targets and the discovery of new chemotherapeutic agents are urgently required. Metalo- aminopeptidases are promising targets in parasitic infections. They participate in crucial processes for parasite growth and pathogenesis. OBJECTIVE: In this review, we describe the structural, functional and kinetic properties, and inhibitors, of several parasite metalo-aminopeptidases, for their use as targets in parasitic diseases. CONCLUSION: Plasmodium falciparum M1 and M17 aminopeptidases are essential enzymes for parasite development, and M18 aminopeptidase could be involved in hemoglobin digestion and erythrocyte invasion and egression. Trypanosoma cruzi, T. brucei and Leishmania major acidic M17 aminopeptidases can play a nutritional role. T. brucei basic M17 aminopeptidase down-regulation delays the cytokinesis. The inhibition of Leishmania basic M17 aminopeptidase could affect parasite viability. L. donovani methionyl aminopeptidase inhibition prevents apoptosis but not the parasite death. Decrease in Acanthamoeba castellanii M17 aminopeptidase activity produces cell wall structural modifications and encystation inhibition. Inhibition of Babesia bovis growth is probably related to the inhibition of the parasite M17 aminopeptidase, probably involved in host hemoglobin degradation. Schistosoma mansoni M17 aminopeptidases inhibition may affect parasite development, since they could participate in hemoglobin degradation, surface membrane remodeling and eggs hatching. Toxoplasma gondii M17 aminopeptidase inhibition could attenuate parasite virulence, since it is apparently involved in the hydrolysis of cathepsin Cs- or proteasome-produced dipeptides and/or cell attachment/invasion processes. These data are relevant to validate these enzymes as targets.
Assuntos
Doenças Transmissíveis , Parasitos , Toxoplasma , Animais , Humanos , Aminopeptidases , Parasitos/metabolismo , Plasmodium falciparumRESUMO
BACKGROUND: Human infectious diseases caused by bacteria are a worldwide health problem due to the increased resistance of these microorganisms to conventional antibiotics. For this reason, the identification of novel molecular targets and the discovery of new antibacterial compounds are urgently required. Metalo-aminopeptidases are promising targets in bacterial infections. They participate in crucial processes for bacterial growth and pathogenesis, such as protein and peptide degradation to supply amino acids, protein processing, access to host tissues, cysteine supply for redox control, transcriptional regulation, site-specific DNA recombination, and hydrogen sulfide production. Although several of these enzymes are not essential, they are required for virulence and maximal growth in conditions of nutrient limitation and high temperatures. OBJECTIVE: In this review, we describe the structural, functional, and kinetic properties of some examples of bacterial metalo-aminopeptidases, in the context of their use as antibacterial targets. In addition, we present some inhibitors reported for these enzymes. CONCLUSION: It is necessary to conduct a meticulous work to validate these peptidases as good/bad targets and to identify inhibitors with potential therapeutic use.
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Doenças Transmissíveis , Sulfeto de Hidrogênio , Aminopeptidases , Antibacterianos/farmacologia , Bactérias/metabolismo , Cisteína , DNA , Humanos , Peptídeo Hidrolases , PeptídeosRESUMO
Contamination by heavy metal ions, particularly in water resources, is a severe environmental problem. In this study, the interaction of metal ions, namely, Cadmium Cd(II), Mercury Hg(II), and Lead Pb(II), on lignin matrices was investigated based on theoretical calculations. Binding energy (ΔEBind) values proved that the Pb(II) interacted better with lignin matrices than Cd(II) or Hg(II), having energy values between -8.4 kcal mol-1 to -20.2 kcal mol-1. The Gibbs energy (ΔG) and enthalpy (ΔH) values for Pb(II) were <0, indicating that the process was spontaneous and released heat. However, the lignin matrices studied in this work did not interact efficiently with Cd(II) and Hg(II) ions because almost all ΔEBind, ΔG, and ΔH values were positive. The bond length of the interaction proved that the Pb ions yielded the smallest values, ratifying the values for the interaction energy. Analyses based on the quantum theory of atoms in molecules showed that the interactions between Pb(II) and the matrices were partially covalent, whereas the interactions of Cd(II) and Hg(II) were predominantly electrostatic, justifying the positive values of ΔEBind, ΔG, and ΔH. The natural bond orbital results showed that the ligand orbitals of the matrix interacted with the lone pair antibonding orbital (LP*) of the metal ions. The theoretical results of the study show the possibility of applying lignin to remove heavy metal ions, especially Pb, and providing information for research related to wastewater treatment.
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Mercúrio , Metais Pesados , Adsorção , Cádmio , Íons , Cinética , Chumbo , LigninaRESUMO
Three photobicyclized benzodithienoquinolizinium tetrafluoroborates (BPDTQBF4) were prepared and evaluated by UV-Vis and fluorescence spectral, electrochemical analysis, and by theoretical calculations as possible organic n-type semiconductors. Evaluation and comparison of their LUMO levels, HOMO-LUMO energy gaps as monomeric and π-stacked dimers with those of other materials, suggest their potential as organic n-type semiconductors. Calculations of their relative charge carrier mobilities confirmed this potential for one derivative with a long (C-14) alkyl chain appended to the polycyclic planar π-system.
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In this study, a background electrolyte capable to separate and quantify inorganic cations in high ionic strength samples by UV-absorption indirect detection was designed. In this regard, the four most abundant monovalent and divalent cations in earth crust (K+, Na+, Ca+2, Mg+2) were selected as model compounds. A group of small carboxylic acids and, several toluidines and pyridines were evaluated as mild strength complexing agents and chromophoric probes, respectively. The optimized background electrolyte was composed of 200 mM 2,4,6-trimethylpyridine as the chromophoric probe, 250 mM lactic acid as the weak complexing agent and pH buffering reagent (adjusted to pH 4.5), and 5% v/v methanol as organic solvent modifier. Based on a minimum number of components, it provided outstanding separation performance in less than 4 min in a wide linear dynamic range (10 - 2500 µg·mL-1). Performances were contrasted against a reference method based on conductometric detection. Furthermore, studies of separation efficiency and peak shape were carried out at different analyte concentrations in high electric conductivity solutions. The herein developed method demonstrated exceptional features in terms of limits of detection (~10 µg·mL-1), resolution, speed of analysis, sensitivity and peak capacity in high electric conductivity samples. Moreover, the method was successfully applied to high ionic strength samples such as rock digest, sea water, soy sauce and isotonic drinks.
Assuntos
Cátions/análise , Eletrólitos/química , Eletroforese Capilar/métodos , Espectrofotometria Ultravioleta/métodos , Ácido Láctico/química , Limite de Detecção , Metanol/química , Concentração Osmolar , Piridinas/químicaRESUMO
This study investigated the influence of cation type on the sodium deactivation of Brazilian bentonite varieties. Four bentonite clays were studied, including three mixed-cationic and one magnesium. Swelling and the main exchangeable cations (Na+, K+, Mg2+ and Ca2+) were the main evaluation parameters in this study. Periodic washes of the sodium-activated bentonites were performed based on the hypothesis that a possible desorption of the cations (primarily Na+) could cause the deactivation. Sodium activation was monitored using XRD measurements and an increase in swelling. Sodium deactivation was observed and monitored via a decrease in swelling. Positive and negative effects, caused by the proportions of the cations and the dominance of Mg2+, were emphasized by the set of cationically different samples applied in this study, which helped to answer the influence of main exchangeable cations, specially Mg2+, on the deactivation process.
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This paper investigated the effect of calcium addition on the formation and properties of aerobic granules under high (conventional SBR) and low (simultaneous fill/draw SBR) selection pressure. Additionally, the simultaneous removal of carbon, nitrogen, and phosphorus, and the operational stability were assessed. The conventional SBRs showed earlier granule development (20 days) than the simultaneous fill/draw SBRs. The effect of calcium on granulation was more accentuated in conventional SBRs, forming larger granules in a shorter interval of time due to the higher EPS production. Additionally, higher amounts of calcium were found in the EPS matrix, mainly during the formation of granules. The operation regime and the addition of calcium did not affect the removal of carbon, nitrogen, and phosphorus. However, they both influenced the granulation time, settleability characteristics, size, and granule composition.
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Cálcio , Esgotos , Aerobiose , Reatores Biológicos , Nitrogênio , Fósforo , Eliminação de Resíduos LíquidosRESUMO
Interest in tumor cell mitochondria as a pharmacological target has been rekindled in recent years. This attention is due in part to new publications documenting heterogenous characteristics of solid tumors, including anoxic and hypoxic zones that foster cellular populations with differentiating metabolic characteristics. These populations include tumor-initiating or cancer stem cells, which have a strong capacity to adapt to reduced oxygen availability, switching rapidly between glycolysis and oxidative phosphorylation as sources of energy and metabolites. Additionally, this cell subpopulation shows high chemo- and radioresistance and a high capacity for tumor repopulation. Interestingly, it has been shown that inhibiting mitochondrial function in tumor cells affects glycolysis pathways, cell bioenergy, and cell viability. Therefore, mitochondrial inhibition may be a viable strategy for eradicating cancer stem cells. In this context, medicinal chemistry research over the last decade has synthesized and characterized "vehicles" capable of transporting novel or existing pharmacophores to mitochondrial tumor cells, based on mechanisms that exploit the physicochemical properties of the vehicles and the inherent properties of the mitochondria. The pharmacophores, some of which have been isolated from plants and others, which were synthesized in the lab, are diverse in chemical nature. Some of these molecules are active, while others are prodrugs that have been evaluated alone or linked to mitochondria-targeted agents. Finally, researchers have recently described drugs with well-proven safety and efficacy that may exert a mitochondria-specific inhibitory effect in tumor cells through noncanonical mechanisms. The effectiveness of these molecules may be improved by linking them to mitochondrial carrier molecules. These promising pharmacological agents should be evaluated alone and in combination with classic chemotherapeutic drugs in clinical studies.
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Antineoplásicos , Portadores de Fármacos , Glicólise/efeitos dos fármacos , Mitocôndrias/metabolismo , Neoplasias , Fosforilação Oxidativa/efeitos dos fármacos , Antineoplásicos/química , Antineoplásicos/uso terapêutico , Sobrevivência Celular/efeitos dos fármacos , Portadores de Fármacos/química , Portadores de Fármacos/uso terapêutico , Resistencia a Medicamentos Antineoplásicos/efeitos dos fármacos , Humanos , Mitocôndrias/patologia , Neoplasias/tratamento farmacológico , Neoplasias/metabolismo , Neoplasias/patologia , Tolerância a Radiação/efeitos dos fármacosRESUMO
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)
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 AmônioRESUMO
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)
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 AmônioRESUMO
Gas-phase interactions between Ba2+ and deprotonated cytosine (C(-H) ) were studied in [C(-H) Ba]+ and [C(-H) BaC]+ complexes by IRMPD spectroscopy coupled to tandem mass-spectrometry in combination with DFT calculations. For the [C(-H) BaC]+ complex only one [C(-H) KAN1O-Ba-Canti ]+ isomer was found, although the presence of another structure cannot be excluded. This isomer features a central tetracoordinated Ba2+ that simultaneously interacts with keto-amino [C(-H) ]- deprotonated on N1 and neutral keto-amino C. Both moieties are in different planes as a consequence of an additional NH O=C hydrogen bond between C and [C(-H) ]- . A sequential IRMPD dynamics is observed in this complex. For the [C(-H) Ba]+ complex produced by electrospray ionization two isomers ([C(-H) KAN1OBa]+ and [C(-H) KAN3OBa]+ ) were identified, in which Ba2+ interacts simultaneously with the C=O group and the N1 or N3 atom of the keto-amino [C(-H) ]- , respectively. A comparison with the related [C(-H) Pb]+ complex (J.â Y. Salpin etâ al., Chem. Phys. Chem. 2014, 15, 2959-2971) is also presented.
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Juveniles of the shrimp Litopenaeus vannamei (3.3⯱â¯0.4â¯g) were exposed separately to nitrite (0.0, 1.1, 2.6, and 5.3â¯mg/L nitrogen as nitrite [NO2--N]) and nitrate (0, 90, 225 and 400â¯mg/L nitrogen as nitrate [NO3--N]) concentrations equivalent to 0, 10, 25, and 50% of the LC50-96â¯h value of NO2--N and NO3--N in low salinity water (3â¯g/L). Shrimps responded to nitrite and nitrate according to changes in oxyhemocyanin, glucose, lactate and ion levels in the hemolymph after 6, 12, 24, and 48â¯h of exposure. Oxyhemocyanin levels decreased with increasing nitrite and nitrate levels and were higher at 50% exposure to the contaminants. Compared to the control, glucose and lactate increased significantly at 50% exposure to nitrite and nitrate, particularly at 12 and 24â¯h. Na+ in the hemolymph changed with nitrite and nitrate, while K+ only changed Ëwith nitrite.
Assuntos
Hemolinfa/efeitos dos fármacos , Nitratos/toxicidade , Nitritos/toxicidade , Penaeidae/efeitos dos fármacos , Poluentes Químicos da Água/toxicidade , Animais , Glucose/metabolismo , Hemocianinas/metabolismo , Hemolinfa/metabolismo , Ácido Láctico/metabolismo , Penaeidae/metabolismo , Potássio/metabolismo , Salinidade , Sódio/metabolismoRESUMO
Subunit vaccines rely on adjuvants carrying one or a few molecular antigens from the pathogen in order to guarantee an improved immune response. However, to be effective, the vaccine formulation usually consists of several components: an antigen carrier, the antigen, a stimulator of cellular immunity such as a Toll-like Receptors (TLRs) ligand, and a stimulator of humoral response such as an inflammasome activator. Most antigens are negatively charged and combine well with oppositely charged adjuvants. This explains the paramount importance of studying a variety of cationic supramolecular assemblies aiming at the optimal activity in vivo associated with adjuvant simplicity, positive charge, nanometric size, and colloidal stability. In this review, we discuss the use of several antigen/adjuvant cationic combinations. The discussion involves antigen assembled to 1) cationic lipids, 2) cationic polymers, 3) cationic lipid/polymer nanostructures, and 4) cationic polymer/biocompatible polymer nanostructures. Some of these cationic assemblies revealed good yet poorly explored perspectives as general adjuvants for vaccine design.
RESUMO
Since phosphate is strongly related to eutrophication of environmental waters, several research groups quest for materials that can efficiently remove phosphate from wastewaters before it contaminates lakes and reservoirs. In the present work, a commercial clay mineral (K10 montmorillonite) modified with Fe3+ polyhydroxy cations was investigated as an adsorbent for phosphate. The incorporation of the polycations did not alter the main conformational characteristics of the montmorillonite, as verified by specific surface area measurements, X-ray diffractometry, FTIR, electron microscopy, and zeta potential titrations. On the other hand, the materials supporting Fe3+ polyhydroxy cations exhibited a significant enhancement of adsorption capacity, as determined by Langmuir-Freundlich isotherms, from 39 ± 2 to 104 ± 15 µmol g-1. The different ratios of OH- to Fe3+ did not affect the adsorption capacities. The adsorption kinetics was best described by the pseudo 2nd order model, approaching the equilibrium after 120 min of contact time. A variation of pH between 4.6 and 8.5 did not affect the adsorption percentages. The adsorption capacities increased with the increase of the ionic strength, thus suggesting that the formation of inner-sphere complexes prevails over electrostatic interactions as the adsorption mechanism. The materials removed phosphate from three polluted water samples having phosphate concentrations between 0.0919 and 1.211 mg L-1. The remaining phosphate concentration was below the limit of quantification of the analytical method (0.063 mg L-1 in P, or 2.0 µmol L-1). The presence of 10 mg L-1 humic of fulvic acid did not affect the performance of the materials. In conclusion, the modification of clay minerals with Fe3+ polyhydroxy cations is useful in producing low-cost adsorbents for phosphate.