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1.
Rev. bras. pesqui. méd. biol ; Braz. j. med. biol. res;55: e12272, 2022. tab, graf
Artigo em Inglês | LILACS-Express | LILACS | ID: biblio-1403904

RESUMO

The study of the interaction of synthetic protoporphyrin IX (PpIXs) and protoporphyrin IX extracted from Harderian glands of ssp Rattus novergicus albinus rats (PpIXe) with bovine serum albumin (BSA) was conducted in water at pH 7.3 and pH 4.5 by optical absorption and fluorescence spectroscopies. PpIXs is present as H- and J-aggregates in equilibrium with themselves and with monomers. The PpIXs charge is 2− at pH 7.3 and 1− at pH 4.5. This increases its aggregation at pH 4.5 and shifts the equilibrium in favor of J-aggregates. In spite of electrostatic attraction at pH 4.5, where BSA is positive, the binding constant (Kb) of PpIXs to BSA is 20% less than that at pH 7.3, where BSA is negative. This occurs because higher aggregation of PpIXs at pH 4.5 reduces the observed Kb value. At both pHs, water-soluble PpIXe exists in the monomeric form with the charge of 1− and its Kb exceeds that of PpIXs. At pH 4.5, its Kb is 12 times higher than that at pH 7.3 due to electrostatic attraction between the positively charged BSA and the negatively charged PpIXe. The higher probability of PpIXe binding to BSA makes PpIXe more promising as a fluorescence probe for fluorescence diagnostics and as a photosensitizer for photodynamic therapy. The existence of PpIXe in the monomeric form can explain its faster cell internalization. Aggregation reduces quantum yields and lifetimes of the PpIXs excited states, which explains higher phototoxicity of PpIXe toward malignant cells compared with PpIXs.

2.
Artigo em Inglês | MEDLINE | ID: mdl-29524745

RESUMO

The bioactivity of propolis against several pathogens is well established, leading to the extensive consumption of that bee product to prevent diseases. Brazilian green propolis, collected by the species Apis mellifera, is one of the most consumed in the world. The chemical composition of green propolis is complex and it has been shown that it displays antioxidant, antimicrobial, anti-inflammatory and antitumor activities, especially due to the high content of Artepillin C. The molecule is a derivative of cinnamic acid with two prenylated groups, responsible for the improvement of the affinity of the compound for lipophilic environment. A carboxylic group (COOH) is also present in the molecule, making it a pH-sensitive compound and the pH-dependent structure of Artepillin C, may modulate its biological activity related to interactions with the cellular membrane of organisms and tissues. Molecular properties of Artepillin C on aqueous solution were examined by optical absorption, steady state and time-resolved fluorescence spectroscopies. Acid-base titration based on the spectral position of the near UV absorption band, resulted in the pKa value of 4.65 for the carboxylic group in Artepillin C. In acidic pH, below the pKa value, an absorption band raised around 350nm at Artepillin C concentration above 50µM, due to aggregation of the molecule. In neutral pH, with excitation at 310nm, Artepillin C presents dual emission at 400 and 450nm. In pH close to the pKa, the optical spectra show contribution from both protonated and deprotonated species. A three-exponential function was necessary to fit the intensity decays at the different pHs, dominated by a very short lifetime component, around 0.060ns. The fast decay resulted in emission before fluorescence depolarization, and in values of fluorescence anisotropy higher than could be expected for monomeric forms of the compound. The results give fundamental knowledge about the protonation-deprotonation state of the molecule, that may be relevant in processes mediated by biological membranes.


Assuntos
Fenilpropionatos/química , Anisotropia , Concentração de Íons de Hidrogênio , Própole/química , Espectrometria de Fluorescência , Espectrofotometria/métodos
3.
Braz. J. Pharm. Sci. (Online) ; 54(2): e00070, 2018. tab, graf
Artigo em Inglês | LILACS | ID: biblio-951927

RESUMO

ABSTRACT The aim of the present study was to investigate the effect of donor pH on the transdermal permeability of the model drugs across rat skin and also to determine the major route of transport of the drugs. Weakly acidic drugs (partition coefficient) ibuprofen (3.6), aceclofenac (3.9), glipizide (1.9) and weakly basic drugs olanzapine (3.6), telmisartan (6.0), and sildenafil citrate (1.9) were selected for the study. The ex vivo permeation studies of these drugs at different donor pH (pH - 1.2, 4, 5, 6.8, 7.4, and 8) using Franz diffusion cell (area, 7.54 cm2) has shown a pH-dependent permeability. Among these drugs the weakly acidic drugs has shown higher permeation rates compared to the weakly basic drugs. The permeability coefficient and the distribution coefficient of the weakly basic drugs increased on increasing the pH whereas the weakly acidic drugs showed an inverse relation. The weakly basic drugs also showed an increase in permeation with increase in the fraction of unionized species indicating dominance of transcellular route of permeation. With an exception of sildenafil citrate, a weakly basic salt form of the drug which showed a high permeation value at pH 7.4 where 57% of the drug was unionized, indicating the involvement of both paracellular and transcellular route in its permeation.


Assuntos
Animais , Masculino , Ratos , Aminoácidos Acídicos/análise , Sistemas de Transporte de Aminoácidos Básicos/análise , Concentração de Íons de Hidrogênio/efeitos dos fármacos , Pele , Solubilidade , Preparações Farmacêuticas/análise
4.
Biophys Rev ; 9(5): 699-728, 2017 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-28921104

RESUMO

pH is a critical parameter for biological and technological systems directly related with electrical charges. It can give rise to peculiar electrostatic phenomena, which also makes them more challenging. Due to the quantum nature of the process, involving the forming and breaking of chemical bonds, quantum methods should ideally by employed. Nevertheless, due to the very large number of ionizable sites, different macromolecular conformations, salt conditions, and all other charged species, the CPU time cost simply becomes prohibitive for computer simulations, making this a quite complex problem. Simplified methods based on Monte Carlo sampling have been devised and will be reviewed here, highlighting the updated state-of-the-art of this field, advantages, and limitations of different theoretical protocols for biomolecular systems (proteins and nucleic acids). Following a historical perspective, the discussion will be associated with the applications to protein interactions with other proteins, polyelectrolytes, and nanoparticles.

5.
Ci. Rural ; 31(6)2001.
Artigo em Português | VETINDEX | ID: vti-703904

RESUMO

The metals bioaccumulation in microganisms is mainly a result of superficial phenomena, occurring adsoption, in a stoychometric way, with the anionic radicals of cellular walls followed or not by precipitation of metals. To study the sorption of metals by live bacteria, the Cu2+ and Mn2+ taken up by a Bacillus sp. and a Pseudomonas sp., were quantified isolated from weath rizosphere, from a cloride solution of metals resting in the supernatant, after centrifugation. A completely randomized experimental design was used, with 3 repetitions. The effect of Cu2+ and Mn2+ contents, pH and time of bacterial growth were tested. Bacillus sorbed more Cu2+ and Mn2+ than Pseudomonas in all concentrations of those metals. Cu2+ sorption by both bacteria showed more increase than Mn2+ with rising those metals content in the solution. Alteration of pH from 5,0 to 3,0 reduced the metal sorption. With 90 hour cultivation time, Pseudomonas showed more Cu2+ and Mn2+ sorption than with 16 hour cultivation time. The results agree with the colloids cations exchange phenomena.


A bioacumulação de metais por microrganismos se deve principalmente a fenômenos de superfície, ocorrendo adsorção, de forma estequiométrica, com os radicais aniônicos dos envoltórios celulares, seguido ou não de precipitação dos metais. Para estudar condicionantes da sorção de metais por bactérias vivas, quantificou-se o Cu2+ e Mn2+ retirados por um Bacillus sp. e uma Pseudomonas sp., isolados da rizosfera de trigo, de uma solução de cloreto dos metais, determinando-se a quantidade de metal restante no sobrenadante, após centrifugação. Usou-se delineamento experimental inteiramente casualizado, com três repetições. Ensaiaram-se efeito dos teores de Cu2+ e Mn2+, do pH e do tempo de crescimento bacteriano. O Bacillus sorveu mais Cu2+ e Mn2+ do que Pseudomonas. em todas as concentrações desses metais. A sorção de Cu2+ por ambas as bactérias apresentou maiores incrementos do que Mn2+ com aumento dos teores desses metais na solução. A alteração do pH 5,0 para 3,0 diminuiu a sorção dos dois metais. Com o tempo de cultivo de 90 horas a Pseudomonas apresentou maior sorção de cobre e de manganês do que no tempo de 16 horas. Os resultados obtidos assemelham-se aos fenômenos de troca de cátions em colóides.

6.
Artigo em Português | LILACS-Express | VETINDEX | ID: biblio-1475669

RESUMO

The metals bioaccumulation in microganisms is mainly a result of superficial phenomena, occurring adsoption, in a stoychometric way, with the anionic radicals of cellular walls followed or not by precipitation of metals. To study the sorption of metals by live bacteria, the Cu2+ and Mn2+ taken up by a Bacillus sp. and a Pseudomonas sp., were quantified isolated from weath rizosphere, from a cloride solution of metals resting in the supernatant, after centrifugation. A completely randomized experimental design was used, with 3 repetitions. The effect of Cu2+ and Mn2+ contents, pH and time of bacterial growth were tested. Bacillus sorbed more Cu2+ and Mn2+ than Pseudomonas in all concentrations of those metals. Cu2+ sorption by both bacteria showed more increase than Mn2+ with rising those metals content in the solution. Alteration of pH from 5,0 to 3,0 reduced the metal sorption. With 90 hour cultivation time, Pseudomonas showed more Cu2+ and Mn2+ sorption than with 16 hour cultivation time. The results agree with the colloids cations exchange phenomena.


A bioacumulação de metais por microrganismos se deve principalmente a fenômenos de superfície, ocorrendo adsorção, de forma estequiométrica, com os radicais aniônicos dos envoltórios celulares, seguido ou não de precipitação dos metais. Para estudar condicionantes da sorção de metais por bactérias vivas, quantificou-se o Cu2+ e Mn2+ retirados por um Bacillus sp. e uma Pseudomonas sp., isolados da rizosfera de trigo, de uma solução de cloreto dos metais, determinando-se a quantidade de metal restante no sobrenadante, após centrifugação. Usou-se delineamento experimental inteiramente casualizado, com três repetições. Ensaiaram-se efeito dos teores de Cu2+ e Mn2+, do pH e do tempo de crescimento bacteriano. O Bacillus sorveu mais Cu2+ e Mn2+ do que Pseudomonas. em todas as concentrações desses metais. A sorção de Cu2+ por ambas as bactérias apresentou maiores incrementos do que Mn2+ com aumento dos teores desses metais na solução. A alteração do pH 5,0 para 3,0 diminuiu a sorção dos dois metais. Com o tempo de cultivo de 90 horas a Pseudomonas apresentou maior sorção de cobre e de manganês do que no tempo de 16 horas. Os resultados obtidos assemelham-se aos fenômenos de troca de cátions em colóides.

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