Magnetic nanoparticles hyperthermia in a non-adiabatic and radiating process.

We investigate the magnetic nanoparticles hyperthermia in a non-adiabatic and radiating process through the calorimetric method. Specifically, we propose a theoretical approach to magnetic hyperthermia from a thermodynamic point of view. To test the robustness of the approach, we perform hyperthermia experiments and analyse the thermal behavior of magnetite and magnesium ferrite magnetic nanoparticles dispersed in water submitted to an alternating magnetic field. From our findings, besides estimating the specific loss power value from a non-adiabatic and radiating process, thus enhancing the accuracy in the determination of this quantity, we provide physical meaning to a parameter found in literature that still remained not fully understood, the effective thermal conductance, and bring to light how it can be obtained from experiment. In addition, we show our approach brings a correction to the estimated experimental results for specific loss power and effective thermal conductance, thus demonstrating the importance of the heat loss rate due to the thermal radiation in magnetic hyperthermia.

Anionic and cationic drug sorption on interpolyelectrolyte complexes.

Interpolyelectrolyte complexes of chitosan and poly(sodium 4-styrenesulfonate) [NaPSS] were synthesized and obtained in the form of solid particles, with two different sulfonate to aminium molar ratios: 0.7, resulting in particles with positive zeta potential (IPEC+), and 1.4, yielding particles with negative zeta potential (IPEC-). Both particles were characterized as potential drug sorbents using differently charged drugs: sodium cromoglycate (negatively charged), and tetracycline hydrochloride (positively charged). The adsorption isotherm for cromoglycate and tetracycline on IPEC+ was adequately described by the Langmuir model, while the IPEC- sorption of tetracycline followed the Redlich-Peterson isotherm without the occurrence of cromoglycate sorption. The sorption kinetics consisted of two processes, one fast and the other slow, which were correlated to purely surface-related interactions and processes that resulted in diffusion and/or destruction/rearrangement on the particle surface and subsurface, respectively. Charge build up equilibrium and kinetics were also monitored via zeta potential measurements, and the differences between mass drug uptake and particle charging were used to propose adsorption mechanisms for the systems studied in this work.

[Diagnostic value of a predictive model for complete ruptures of the rotator cuff associated to subacromial impingement]. / Valor diagnóstico de un modelo de predicción clínico-radiográfico para rupturas completas del manguito de los rotadores por pinzamiento subacromial.

Pathology related to the rotator cuff remains among the most prevalent musculoskeletal diseases. There is an increasing need for imaging studies (MRI, US, arthroscopy) to test the diagnostic performance of the medical history and physical examination. OBJECTIVE: To prove the diagnostic value of a clinical-radiographic predictive model to find complete ruptures of the rotator cuff. MATERIAL AND METHODS: Descriptive, observational, prospective, transversal and analytical study. Fifty-five patients with preoperative shoulder pain were evaluated with 13 predictive variables: age > 50 years, nocturnal pain, muscle weakness, clinical signs of Neer, Hawkins, Jobe, external rotation lag (ERLS), belly-press, bear hug, and lift-off, radiographic measurement of subacromial space, acromial index and critical shoulder angle. Sensitivity, specificity, and positive and negative predictive values were measured in each variable, comparing the results of each one against the postoperative findings. RESULTS: Of the 55 patients evaluated, 42 had a complete rupture of the rotator cuff in the postoperative period. The eight variables with a higher diagnostic value were selected and a ROC curve was performed, providing an area under the curve of 0.88. CONCLUSIONS: This predictive model uses eight variables (age > 50 years, nocturnal pain, muscle weakness, Jobe, Hawkins, ERLS, subacromial space ≤ 6 mm, and critical shoulder angle > 35°), which together add the predictive value of 0.88 (AUC) to diagnose complete ruptures of the supraspinatus tendon.

La patología relacionada al manguito de los rotadores permanece entre las enfermedades musculoesqueléticas más prevalentes. Hay una creciente necesidad de estudios de imagen (RMN, US, artroscopía) para probar el rendimiento diagnóstico de la historia clínica y el examen físico. Objetivo: Demostrar el valor diagnóstico de un modelo predictor clínico-radiográfico para rupturas completas del manguito de los rotadores. Material y métodos: Estudio descriptivo, observacional, prospectivo, transversal, analítico. Se evaluaron 55 pacientes con dolor de hombro en forma preoperatoria con 13 variables de predicción: edad > 50 años, dolor nocturno, debilidad muscular, signos clínicos de Neer, Hawkins, Jobe, caída de la rotación externa, Napoleón, abrazo del oso, Gerber; medición radiológica del espacio subacromial, índice acromial y ángulo crítico del hombro. En cada variable se midió sensibilidad-especificidad, valor predictivo positivo y negativo. Se compararon los resultados de cada variable para diagnosticar rupturas del manguito de los rotadores contra los hallazgos postoperatorios. Resultados: De los 55 pacientes evaluados, 42 presentaron ruptura completa del mango rotador en el postoperatorio. Se seleccionaron las ocho variables con mayor valor diagnóstico y se realizó una curva ROC, proporcionando un área bajo la curva de 0.88. Conclusiones: Este modelo de predicción emplea ocho variables (edad > 50 años, dolor nocturno, debilidad muscular, caída de la rotación externa, Jobe, Hawkins, espacio subacromial ≤ 6 mm y ángulo crítico del hombro > 35°) que en conjunto suman el valor predictivo de 0.88 (AUC) para diagnosticar rupturas completas del tendón supraespinoso.

Rheology and dynamic light scattering of octa-ethyleneglycol-monododecylether/chitosan solutions.

In this work we used rheometry and DLS to probe relaxation phenomena in solutions of chitosan and octa-ethyleneglycol-monododecylether. The dispersions had a marked pseudoplastic behavior, which became less evident, as surfactant concentration was increased. Arrhenius plots showed that systems with surfactant presented a characteristic temperature at which apparent enthalpy of activation (varying from 3 to 40 kJ mol(-1)) changed: this change was correlated to a possible transition of colloidal aggregates to a wormlike configuration. DLS intensity correlation functions were described by KWW equation: pure chitosan solutions had relaxation rate distributions centered at a characteristic relaxation rate around 4.6×10(-6) µS(-1); as surfactant was added, a new component, with a faster characteristic relaxation rate with a magnitude order of 10(-3) µs(-1), appeared. It was shown that the dependence between these relaxation rates and surfactant concentration could be used to describe DLS-related relaxation phenomena as an Arrhenius-activated process, agreeing with results obtained using rheometry.

Human immunodeficiency virus-associated depression: contributions of immuno-inflammatory, monoaminergic, neurodegenerative, and neurotrophic pathways.

In the era of greatly improved pharmacological treatment of HIV infection through highly active antiretroviral therapy (HAART), HIV patients experience reduced viral loads, reduced opportunistic infections, increased CD4+ T cell count, and greater life expectancy. Although life expectancy is increased, patients often develop neurological disturbances that may persist for long periods, seriously jeopardizing quality of life and adherence to the medication protocols of HAART. For these reasons, HIV-associated neurological disorders have gained importance in both clinical and basic investigations of HIV infection. Depression is the most prevalent neuropsychiatric disorder among people living with HIV. In this review, we discuss how HIV can predispose infected individuals to depression by several interrelated mechanisms. These include inducing chronic elevation of cytokines through activation of microglia and astrocytes; decreasing monoaminergic function; inducing neurotoxicity, especially in dopaminergic neurons; and reducing brain-derived neurotrophic factor. These viral pathways interact with psychosocial factors to create the depressive state. HIV depression has a great impact on quality of life and implementation of antiretroviral therapy, and thus, recognition of these modes of action is significant for understanding HIV neuropathology and for selecting modalities for pharmacologic treatment.

Equilibrium and kinetic aspects of sodium cromoglycate adsorption on chitosan: mass uptake and surface charging considerations.

Chitosan has more and more been suggested as a material for use as adsorbent in the treatment of effluents as well as in the synthesis of drug-loaded nanoparticles for controlled release. In both cases, a good understanding of the process of adsorption, both kinetically and in terms of equilibrium, has an importance of its own. In this manuscript we study the interaction between sodium cromoglycate, a drug used in asthma treatment, and chitosan. Equilibrium experiments showed that Sips (or Freundlich-Langmuir) isotherm described well the resultant data and adsorption possibly occurred as in multilayers. A model based on ordinary reaction-rate theory, compounded of two processes, each one with a correlated velocity constant, described the kinetics of sorption. Kinetic and equilibrium data suggested the possibility of surface rearrangement, favored by the increase of temperature.

Tetracycline adsorption on chitosan: a mechanistic description based on mass uptake and zeta potential measurements.

Adsorption phenomena occurring at the solid/liquid interface of chitosan particles are of extreme importance in the kinetics of drug release/upload as well as in effluent treatment by adsorption. In this work, equilibrium and kinetic aspects of protonated tetracycline adsorption on chitosan are explored using classic solution depletion method and zeta potential measurements. Equilibrium experiments showed that for solutions with tetracycline initial concentration of ca. 1.2 g L(-1), corresponding to a pH around 3, chitosan structure disrupted, as indicated by an increase in magnitude of tetracycline sorption. Adsorption and zeta potential isotherms before disruption suggested that the process of adsorption had a Langmuir character up to a point at which subsurface was exposed to adsorption; at this point, a second mode of sorption began: zeta potential tended to an equilibrium value, following Sips isotherm and tetracycline sorption had a linear dependence on its continuous phase concentration. The kinetics of tetracycline sorption suggested that sorption of tetracycline was divided between the sorption of protonated and non-protonated tetracycline; tetracycline in its non-protonated form seemed to rule the sorption of tetracycline.

Surface charging and dimensions of chitosan coacervated nanoparticles.

Chitosan nanoparticles have been used in several systems destined to controlled release of active agents. In this manuscript the process of formation of chitosan nanoparticles, obtained employing the coacervation method with sodium sulfate is analyzed using zeta potential and small angle X-ray scattering (SAXS) measurements. Dispersions were obtained at pH=1 and pH=3 and presented a behavior, in terms of surface charging, that was independent of pH. However, SAXS results indicated a dependence of size-related behavior on pH. The difference in terms of behavior was explained through the influence of enthalpic and entropically driven components.

Viscosity-temperature behavior of chitin solutions using lithium chloride/DMA as solvent.

Solutions of chitin in Li(+)/N,N-dimethylacetamide systems were studied via viscometry, using LiCl concentrations of 3% and 5% (m/v) and chitin concentrations ranging from 0.075 to 0.375 gL(-1). The reduced viscosity number versus concentration plot showed a minimum that was related to the formation of Li(+)-OC complex moieties along chitin macromolecular chains. Viscosity behavior was affected by temperature according to the Eyring model: concentration dependence of flow enthalpy of activation was correlated to polymer-polymer interactions and flow entropy of activation to the stiffness of the complexed chitosan macromolecular chain.

Determination of deacetylation degree of chitosan: a comparison between conductometric titration and CHN elemental analysis.

Chitosan is a polysaccharide used in a broad range of applications. Many of its unique properties come from the presence of amino groups in its structure. A proper quantification of these amino groups is very important, in order to specify if a given chitosan sample can be used in a particular application. In this work, a comparison between the determination of chitosan degree of deacetylation by conductometry and CHN elemental analysis was carried out, using a rigorous error analysis. Accurate expressions relating CHN composition, conductometric titration, and degree of deacetylation, in conjunction with their associated errors, were developed and reported in this note. Error analysis showed conductometric analysis as an inexpensive and secure method for the determination of the degree of deacetylation of chitosan.

The kinetics of adsorption of tetracycline on chitosan particles.

Experiments to monitor and characterize the kinetics of adsorption of tetracycline on chitosan particles are reported in this work. The same pseudo-order kinetics that has been widely used for describing the adsorption in systems related to wastewater purification and drug loading was used to treat the present data. As some unexpected results came out from the experiments, it was necessary a detailed deduction for this sort of kinetics to be carried out, so that approximations related to short and long times were obtained. Firstly it was shown that an apparently linear t/q(t) versus t relationship did not imply a pseudo-second-order sorption kinetics, differently of what has been repeatedly reported in the literature. It was found that this misinterpretation could be avoided by using non-linear regression. Finally, the adsorption of tetracycline on chitosan particles was analyzed, using the insights obtained from theoretical analysis, and the parameters generated were used to analyze to adsorption kinetics and to propose an adsorption mechanism.

Chitosan membranes modified by contact with poly(acrylic acid).

In this work chitosan membranes modified by contact with poly(acrylic acid) (PAA) aqueous solution at two different temperatures (25 degrees C and 60 degrees C) were obtained. The pure chitosan (CS) membranes, as well as those treated with PAA (CSPAA_25 and CSPAA_60) were characterized by FTIR-ATR, water sorption capacity, thermal analysis (TG/DTG), and scanning electron microscopy (SEM). In addition, in vitro permeation experiments were carried out using metronidazol and sodium sulfamerazine aqueous solutions at 0.1% and 0.2% as model drugs. FTIR-ATR results showed the presence of absorption bands of NH3+ and COO(-) indicating the formation of a polyelectrolyte complex between chitosan and poly(acrylic acid). The results also indicated that PAA penetrates deeper into the membrane at higher temperature (60 degrees C), forming a thicker complex layer. Polyelectrolyte complex formation as well as the influence of treatment temperature was confirmed by lower hydrophilicity, higher thermal stability, and lower permeability of the treated membranes. The results show that the methodology used is a simple and very efficient way to drastically change some membrane properties, especially their permeability.

Equilibrium and kinetic analysis of methyl orange sorption on chitosan spheres.

Chitosan can be used as adsorbent in the treatment of effluents from the textile industry, especially for negatively charged dyes, due to its cationic polyelectrolyte nature. In this work, the sorption of a model dye, methyl orange, on chitosan hydrobeads is analyzed in terms of equilibrium and kinetic approaches. Equilibrium studies showed that dye adsorption had a mixed Freundlich-Langmuir behavior that had its Langmuir character increased as the pH was increased. In terms of adsorption kinetics, it was found to be of nth-pseudo-order, with fractional n increasing from approximately 2 to approximately 2.5 as pH and initial dye concentration in the continuous phase were increased. The increase in the apparent pseudo-order was related to changes in mathematical approximation for the solution of the sorption rate equation, which were the result of the decrease in the ratio (number of active sites for adsorption)/(number of adsorbate molecules).

Chitosan-poly(acrylic acid) polyelectrolyte complex membranes: preparation, characterization and permeability studies.

Polyelectrolyte complex (PEC) membranes were obtained by mixing solutions of two polymers of opposite charges, chitosan (Chi) and poly(acrylic acid) PAA. Three membranes were obtained: one made of pure chitosan and two membranes with chitosan mixed with PAA at a ratio of 95:5 (one prepared using PAA solution in 3.5% formic acid, named ChiPAA3.5, and another one using a PAA solution in 10% formic acid, named ChiPAA10). The membranes were characterized by swelling experiments, FT-IR spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), mechanical properties and permeability studies in relation to a drug model (sodium sulphamerazine). The calculation of degree of ionization showed that the lower the formic acid concentration was, the higher the PAA dissociation degree. Polyelectrolyte complex formation was characterized by FT-IR. Water uptake results showed that PEC membranes were more hydrophilic than pure chitosan, ChiPAA3.5 being the most. Morphological analysis by SEM and AFM showed that PAA addition changed the membranes morphology, especially for ChiPAA3.5. Mechanical properties indicated that PEC membranes were more rigid than pure chitosan membranes and that the morphology has an influence on tensile strength values. Permeability values decreased with complex formation and were lower for ChiPAA10 than ChiPAA3.5. However, as drug concentration was increased, the difference between the two complex membranes disappeared. The results were discussed considering the drug-membrane interactions. Diffusion coefficient values indicated that ChiPAA3.5 had a higher drug retention capacity than ChiPAA10.

Adsorption of bovine serum albumin on template-polymerized chitosan/poly(methacrylic acid) complexes.

Particulate systems composed of polyelectrolyte complexes (PEC) based on chitosan and poly(methacrylic acid) were obtained via template polymerization. The resultant particles were characterized as having regions with different charge densities: chitosan predominating in the core and poly(methacrylic acid) at the surface, the particles being negatively charged, as a consequence. Albumin was adsorbed on these particles (after cross-linking with glutardialdehyde), and pH was controlled to obtain two conditions: (i) adsorption of positively charged albumin and (ii) adsorption of albumin at its isoelectric point. Adsorption isotherms and zeta-potential measurements showed that albumin adsorption was controlled by hydrogen bonding/van der Waals interactions and that brush-like structures may enhance the adsorption of albumin on these particles. It was also found that shearing can induce desorption of albumin from the PEC surface, depending on the continuous phase albumin concentration.

Effect of molecular weight and ionic strength on the formation of polyelectrolyte complexes based on poly(methacrylic acid) and chitosan.

Chitosan/poly(methacrylic acid) complexes, CS/PMAA, were prepared via dropwise addition of a solution of PMAA to a solution of chitosan in acetic acid 2 wt %. The increase in molecular weight of PMAA inhibited the formation of insoluble complexes, while the increase in ionic strength first favored the formation of the complex followed by inhibiting it at higher concentrations. These observations were related to a description of polyelectrolyte complexation that was strongly dependent on macromolecular dimensions, both in terms of molecular weight and of coil expansion/contraction driven by polyelectrolyte effect.

Permeability studies in chitosan membranes. Effects of crosslinking and poly(ethylene oxide) addition.

Pure chitosan, glutaraldehyde crosslinked chitosan, and a blend of chitosan with poly(ethylene oxide) (PEO) membranes were prepared. The three membranes were characterized in terms of their swelling capacities as well as their permeabilities to a drug model (sulfamerazine sodium salt). For the permeation experiments, the variables analyzed were the type of membrane and the initial drug concentration in the liquid phase (from 0.1% to 1.5%). Permeability coefficients were calculated using UV spectroscopy. The results showed that for the three analyzed membranes, the permeability did not change with time (over the studied time interval). An increase in the permeability for CHI/PEO membranes compared to those made of pure chitosan was also observed, possibly due to microporous region formation and/or crystallinity reduction. For the crosslinked membrane, an even higher increase in the permeability coefficient was observed. In this case, the increase was attributed to free volume variation.