Mauro C. M. Laranjeira

Adsorption of Anionic Dyes on the Biopolymer Chitin

The adsorption of the anionic dyes orange IV, orange G and xylenol orange on chitin was studied, employing the Langmuir isotherm. The adsorption parameters were determined utilizing various linear regressions of the isotherm. The results showed that the adsorption capacity is dependent on pH. In acid pH, the polymer amino groups are protonated and the polymer chain is positively charged, with a predominance of adsorption through ion exchange. Van der Waals adsorption, as well as adsorption through hydrogen bonding, is also likely to occur to some extent. For xylenol orange, a linear regression was found, with an angular coefficient of 0.726 L mg-1. The temperature increase reduces adsorption capacity by chitin, due to the enhancement of the desorption step in the mechanism. DH values of -10.9 kJ mol-1 for orange G and -28.9 kJ mol-1 for orange IV prove the physical nature of the adsorption by these dyes on the chitin surface.

Cross-linked quaternary chitosan as an adsorbent for the removal of the reactive dye from aqueous solutions

Adsorption of reactive orange 16 by quaternary chitosan salt (QCS) was used as a model to demonstrate the removal of reactive dyes from textile effluents. The polymer was characterized by infrared (IR), energy dispersive X-ray spectrometry (EDXS) analyses and amount of quaternary ammonium groups. The adsorption experiments were conducted at different pH values and initial dye concentrations. Adsorption was shown to be independent of solution pH. Three kinetic adsorption models were tested: pseudo-first-order, pseudo-second-order and intraparticle diffusion. The experimental data best fitted the pseudo-second-order model, which provided a constant velocity, k2, of 9.18 x 10(-4)g mg(-1)min(-1) for a 500 mg L(-1) solution and a value of k2, of 2.70 x 10(-5)g mg(-1)min(-1) for a 1000 mg L(-1) solution. The adsorption rate was dependent on dye concentration at the surface of the adsorbent for each time period and on the amount of dye adsorbed. The Langmuir isotherm model provided the best fit to the equilibrium data in the concentration range investigated and from the isotherm linear equation, the maximum adsorption capacity determined was 1060 mg of reactive dye per gram of adsorbent, corresponding to 75% occupation of the adsorption sites. The results obtained demonstrate that the adsorbent material could be utilized to remove dyes from textile effluents independent of the pH of the aqueous medium.

Effect of Crosslinking Agents on Chitosan Microspheres in Controlled Release of Diclofenac Sodium

In this work chitosan microspheres were prepared by the simple coacervation method and crosslinked using epichlorhydrin or glutaraldehyde for the controlled release of diclofenac sodium. The effects of the crosslinking agents on chitosan microspheres over a 12-hour period were assessed with regard to swelling, hydrolysis, porosity, crosslinking, impregnation of diclofenac sodium (DS), and consequently to the release of DS in buffer solutions, simulating the gastrointestinal tract. The degree of swelling varied with the pH for glutaraldehyde chitosan microspheres (GCM) and epichlorhydrin chitosan microspheres (ECM). Partial acid and basic hydrolysis affected the swelling behavior of the GCM matrix. Release kinetics of diclofenac sodium from these matrices were investigated at pH 1.2, 6.8 and 9.0, simulating the gastrointestinal tract conditions. The results indicated that the release mechanism deviated slightly from Fickian transport.

Calcium phosphate biomaterials from marine algae. Hydrothermal synthesis and characterisation

Calcium phosphate compounds such as Hydroxyapatite (HAp) were prepared by hydrothermal synthesis with phycogenic CaCO3 as starting material. Material obtained was characterised by usual methods (XRD, FTIR, TG, N2-adsorption, SEM and EDX) in order to study its physical-chemical characteristics. The prepared HAp showed that it may be suitable for use as a biomaterial.

Sulphoxine immobilized onto chitosan microspheres by spray drying: application for metal ions preconcentration by flow injection analysis

A new chelating resin based on chitosan biopolymer modified with 5-sulphonic acid 8-hydroxyquinoline using the spray drying technique for immobilization is proposed. The chelating resin was characterized by thermogravimetric analysis (TGA) and X-ray diffraction (XRD) and surface area by nitrogen sorption. The efficiency of the chelating resin was evaluated by the preconcentration of metal ions Cu(II) and Cd(II) present in aqueous samples in trace amounts. The metal ions were previously enriched in a minicolumn and the concentrations of the analytes were determined on-line by flame atomic absorption spectrometry (FAAS). The maximum retention for Cu(II) occurred in the pH range 8-10, and for Cd(II) at pH 7. The optimum flow rate for sorption was found to be 7.2mlmin(-1) for the preconcentration of the metal ions. The analytes gave relative standard deviations (R.S.D.) of 0.7 and 0.6% for solutions containing 20mugl(-1) of Cu(II) and 15mugl(-1) of Cd (II), respectively (n=7). The enrichment factors for Cu(II) and Cd (II) were 19.1 and 13.9, respectively, and the limits of detection (LOD) were 0.2mugl(-1) for Cd(II) and 0.3mugl(-1) for Cu(II), using a preconcentration time of 90s (n=11). The accuracy of the proposed method was evaluated by the metal ion recovery technique, in the analysis of potable water and water from a lake, with recoveries being between 97.2 and 107.3%.

Adsorption of calcium ions by graft copolymer of acrylic acid on biopolymer chitin

The graft copolymer of acrylic acid on biopolymer chitin, with 45% grafting efficiency, was used to study the effect of the carboxylic group of the graft copolymer on the metal binding ability of calcium ions in aqueous solution as a function of pH, contact time and metal concentration. The adsorption equilibrium data correlate well with the Langmuir isotherm equation. The maximum adsorption capacities of graft copolymer and chitin were found to be 0.500 ± 0.013 and 0.195 ± 0.005 mmol Ca2+ g−1, respectively, suggesting the effective participation of the carboxylic group in Ca2+ adsorption. The poly(acrylic acid)- grafted chitin is promising as a polymeric matrix to be used in the preparation of new glass ionomer cements.

Development and evaluation of pH-sensitive sodium alginate/chitosan microparticles containing the antituberculosis drug rifampicin.

This paper describes the encapsulation of a high molecular weight molecule rifampicin (RIF) in sodium alginate/chitosan microparticles, which provided controlled-release when evaluated in vitro. The microparticles were prepared by the coacervation technique. To evaluate and select the best encapsulation method two approaches were applied: coacervation (MCP method 1) and impregnation (MCP method 2). The microparticles obtained were analyzed by DSC, DRIFT, XRD and SEM and also the loading efficiency, swelling degree (SD) and in vitro release were determined. The results obtained showed that the alginate/chitosan microparticles represent an efficient system for the controlled-release of RIF. At acidic pH, the release of 20% of the drug occurred in 2h, and at pH6.8 a rapid increase in the release rate was observed up to 100%. The mechanism involved in the release was Super Case II kinetics since n>1 (n=1.09 and 1.13 for microparticles produced by methods 1 and 2, respectively), indicating that the release was related to diffusion, swelling, relaxation and erosion processes. The dissolution efficiencies were similar for both formulations, and the f2 values of ≥50 indicated the similarity between the two profiles, under the assumption of a maximum allowable difference of 10%.

Quitosana: biopolímero funcional com potencial industrial biomédico

The importance of chitosan has grown significantly over the last two decades due to its renewable and biodegradable source, and also because of the recent increase in the knowledge of its functionality in the technological and biomedical applications. The present article reviews the biopolymer chitosan and its derivatives as versatile biomaterials for potential drug delivery systems, as well as tissue engineering applications, analgesia and treatment of arthritis.

Synthesis of calcium-phosphate and chitosan bioceramics for bone regeneration

Bioceramic composites were obtained from chitosan and hydroxyapatite pastes synthesized at physiological temperature according to two different syntheses approaches. Usual analytical techniques (X-ray diffraction analysis, Fourier transformed infrared spectroscopy, Thermo gravimetric analysis, Scanning electron microscopy, X-ray dispersive energy analysis and Porosimetry) were employed to characterize the resulting material. The aim of this investigation was to study the bioceramic properties of the pastes with non-decaying behavior from chitosan-hydroxyapatite composites. Chitosan, which also forms a water-insoluble gel in the presence of calcium ions, and has been reported to have pharmacologically beneficial effects on osteoconductivity, was added to the solid phase of the hydroxyapatite powder. The properties exhibited by the chitosan-hydroxyapatite composites were characteristic of bioceramics applied as bone substitutes. Hydroxyapatite contents ranging from 85 to 98% (w/w) resulted in suitable bioceramic composites for bone regeneration, since they showed a non-decaying behavior, good mechanical properties and suitable pore sizes.

Evaluation of chitosan microparticles containing curcumin and crosslinked with sodium tripolyphosphate produced by spray drying

The aim of this study was to encapsulate curcumin into chitosan, using sodium tripolyphosphate (TPP) as an ionic crosslinker by the spray drying method. The influence of TPP on the properties of the final product, such as solubility, morphology, loading efficiency, thermal behavior, swelling degree and release profiles, was evaluated. The microparticles had a spherical morphology (0.5-20 µm) with no apparent porosity or cracks. Results indicated the formation of a polymeric network, which ensures effective protection for curcumin. Controlled-release studies were carried out at pH 1.2 and 6.8, to observe the influence of pH on curcumin release while the mechanism was analyzed using the Korsmeyer-Peppas equation.