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.

The aim of this study was to impregnate the chelating agent 3,3-bis-N,N,bis-(carboxymethyl)aminomethyl-o-cresolsulfonephthalein in chitosan and to investigate the adsorption of Cu(II) ions. The chemical modification was confirmed by FTIR spectrometry, thermogravimetric analysis (TGA) and energy dispersive x-ray spectroscopy (EDX). The adsorption studies were carried out with Cu(II) ions in a batch process and were shown to be dependent on pH. The adsorption kinetics was tested using three models: pseudo first-order, pseudo second order and intraparticle diffusion. The experimental kinetics data were best fitted with the pseudo second-order model (R² = 0.999), which provided a rate constant, k2, of 1.21 x 10-3 g mg-1 min-1. The adsorption rate depended on the concentration of Cu(II) ions on the adsorbent surface and on the quantity of Cu(II) ions adsorbed at equilibrium. The Langmuir isotherm model provided the best fit for the equilibrium data in the concentration range investigated, with the maximum adsorption capacity being 81.0 mg of Cu(II) per gram of adsorbent, as obtained from the linear equation of the isotherm. Desorption tests revealed that around 90% of the adsorbed metal was removed, using EDTA solution as the eluent. This result suggests that the polymeric matrix can be reused.

Considerable attention has been paid to chitosan and derivatives as efficient adsorbents of pollutants such as metal ions and dyes in aqueous medium. Nevertheless, no report can be found on the remedial actions of chitosan microspheres crosslinked with tripolyphosphate to control acidity, iron (III) and manganese (II) contents in wastewaters from coal mining. In this work, chitosan microspheres crosslinked with tripolyphosphate were used for the neutralization of acidity and removal of Fe (III) and Mn (II) from coal mining wastewaters. The study involved static and dinamic methods. The neutralization capacity of the surface of the static system was 395 mmol of H3O+ per kilogram of microspheres, higher than that of the dynamic one (223 mmol kg-1). The removal of Fe(III) in wastewater was of 100% and that of Mn(II) was 90%.

O sal quaternário de quitosana foi sintetizado com cloreto de glicidil trimetil amônio. A modificação química foi caracterizada por espectrometria no IV, RMN de 13C e ¹H, e mmol/g de grupos quaternários presentes na matriz polimérica por condutimetria. A remoção de Cr (VI), Mo (VI) e Se (VI), em meio aquoso, foi investigada em processo de batelada. A adsorção mostrou ser dependente do pH para o Cr (VI) e Se (VI), com um pH ótimo de adsorção, entre 4,0 a 6,0. Para o Mo (VI) a adsorção manteve-se quase constante no intervalo de pH entre 4,0 e 11,5. O modelo de isoterma de Langmuir descreveu melhor os dados de equilíbrio na faixa de concentração investigada. No presente estudo, um grama do sal quaternário de quitosana reticulado com glutaraldeído adsorveu 68,3 mg de Cr, 63,4 mg de Mo e 90,0 mg de Se. A velocidade de adsorção, no processo, segue a equação cinética de pseudo segunda-ordem, sendo que o equilíbrio para os três íons foi alcançado próximo aos 200 minutos. A análise dispersiva de raios-X para o Cr (VI) mostrou que o principal mecanismo de adsorção é a troca iônica entre os íons Cl- da superfície do polímero pelos oxiânions. O trocador aniônico apresentou a seguinte ordem de seletividade: Cr (VI) > Mo (VI) > Se (VI).

Quaternary chitosan salt was synthesized in the presence of glycidyl trimetyl ammonium chloride. The polymer was characterized by spectroscopic techniques: infrared, 13C and ¹H NMR, while the amount of quaternary ammonium groups was obtained by condutimetry. The removal of Cr (VI), Mo (VI) and Se (VI) from aqueous solutions was carried out in batch adsorption processes. The process seemed to be pH dependent for Cr (VI) and Se (VI) with an optimum pH ranging from 4.0 to 6.0; while for Mo (VI) the adsorption remained almost constant within the range between 4.0 and 11.5. The Langmuir isotherm model provided the best fit of the equilibrium data over the whole concentration investigated. In the experiment one gram of cross-linked quaternary chitosan salt adsorbed 68.3 mg of chromium, 63.4 mg of molybdenum and 90.0 mg of selenium. The adsorption process followed a pseudo second-order kinetic rate equation and the equilibrium regarding the three ions was reached after 200 minutes. The studies from X-ray dispersive energy showed that the main adsorption mechanism is ionic exchange among Cl- groups on the polymer surface by oxyanions from solution and the anionic exchanger showed the following selectivity order: Cr (VI) > Mo (VI) > Se (VI).

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.

Compósitos biocerâmicos foram obtidos a partir de pastas de quitosana e hidroxiapatita, preparadas a temperatura fisiológica seguindo dois métodos diferentes de síntese. As técnicas analíticas usuais (Análise de difração de raios-X, Espectroscopia de absorção no infravermelho com transformada de Fourier, Análise termogravimétrica, Microscopia eletrônica de varredura, Análise por energia dispersiva de raios-X, e Porosimetria) foram empregadas para caracterizar o material resultante. O objetivo deste trabalho foi estudar as propriedades biocerâmicas das pastas relativas ao comportamento de não-desintegração dos compósitos de quitosana-hidroxiapatita. A quitosana, que também forma um gel insolúvel em água na presença de íons cálcio, e tem mostrado possuir efeitos farmacologicamente benéficos na condutividade óssea, foi adicionada à fase sólida do pó de hidroxiapatita. As propriedades exibidas pelos compósitos de quitosana-hidroxiapatita apresentaram características de biocerâmicas empregadas como substitutos de osso. O conteúdo de hidroxiapatita na faixa entre 85 a 98% em peso resultou em compósitos biocerâmicos adequados para regeneração óssea, visto que apresentaram um comportamento de não-desintegração, boas propriedades mecânicas e tamanhos de poros apropriados.

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.

Microesferas de quitosana com grau de desacetilação médio de 85,6% foram enxertadas com poli(ácido acrílico) para aplicação como sistemas de liberação controlada de fármacos. O corante eosina impregnado nas microesferas de quitosana modificada foi utilizado como marcador para estudo in vitro de liberação de fármacos. As microesferas de quitosana foram obtidas pelo método de inversão de fases com NaOH, seguidas de reticulação com glutaraldeído, redução com cianoboroidreto de sódio e enxertia com poli(ácido acrílico) na presença de uma solução de nitrato de cério (IV) amoniacal como iniciador redox. Os estudos in vitro de liberação da eosina a partir de microesferas de quitosana, mostraram que o corante foi liberado em função do tempo a pH 6,8 e 9,8 que simulam as condições fisiológicas do trato gastrointestinal, enquanto que nenhuma eosina foi liberada a pH 1,2.

Chitosan microspheres obtained by coacervation-phase separation, cross-linked with glutaraldehyde and grafted with poly(acrylic acid) were used as the basis of in vitro studies on the controlled release of eosin. Microspheres impregnated with an aqueous solution of the dye depicted a time-dependent release of eosin at pH values of 6.8 and 9.8, typical of the gastrointestinal tract. No eosin release could be observed at 1.2 pH.

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.

Capsules were prepared from chitosan (QTS)-poly(vinyl alcohol) (PVA) blend by saline coacervation and then by formalization. A adsorbent based on chitosan, insoluble on acid solution, was obtained. The morphology, average diameters of QTS/PVA capsules and their pores were studied by using scanning electron microscopy. The entrapment-adsorption of dimethylglioxime and ethylenediaminetetracetate by the capsules were studied. The removal of the ion nickel (II) and copper (II), was more effective than by using unloaded capsules.

RESUMO: Microesferas de quitosana com grau de reticulação de 24% foram empregadas para adsorção dos corantes reativos Azul 2, Preto 5 e Laranja 16. A adsorção dos corantes reativos foi avaliada em função da acidez da solução e do tempo de contato com o adsorvente. A constante de velocidade (k) e a capacidade de adsorção aumentaram com a diminuição do pH. Em pH > 10,0, a adsorção dos corantes praticamente não ocorre, assim soluções neste pH podem ser usadas para dessorver os corantes das microesferas. A principal interação é de natureza eletrostática entre os grupos -NH3+ da quitosana e -SO3- dos corantes.

Microspheres of chitosan with the degree of cross-linking of 24% were used for adsorption of the reactive dyes Blue 2, Black 5 and Orange 16. The adsorption of the reactive dyes on microspheres of cross-linked chitosan was studied. The rate constants and the adsorption capacity were determined with buffered dye solutions at different pH values and a function of the contact time with the chitosan microspheres. At pH > 10.0 the adsorption of dyes practically does not occur and these pH conditions may be used to desorb the dyes from the microspheres. The main interaction of electrostatic nature is due to the binding between -NH3+ groups in chitosan and -SO3- in dyes.

Adsorption of Cu(II), Ni(II), Pb(II) and Zn(II) ions from aqueous solutions by N-(3,4-dihydroxybenzyl) chitosan have been carried out. The Langmuir (L), Freundlich (F), Langmuir - Freundlich (LF), Redlich-Peterson (RP) and Tóth (T) adsorption isotherms models have been applied to fit the experimental data. Nonlinear regression computational program "Enzefitte", which is a library of the more commonly used adsorption isotherm equations for obtaining tabular outuput suitable for plotting theoretical of fitted isotherms, has been used to estimate the adsorption parameters. These parameters were used to calculate the amount adsorbed q calc., a function of concentration (C).

Mostramos neste trabalho alguns detalhes sobre a imobilização de complexos ferrocianeto e ferricianeto sobre a superfície do biopolímero quitosana. Os complexos imobilizados foram caracterizados por eletroquimica, espectrocopia de infravermelho e Mössbauer. Foi observado mudanças nos espectros de infravermelho e Mössbauer, e no voltamogramas cíclicos do material preparado com ferricianeto após exposição a luz do sol. Estas alterações indicam que o ferricianeto sofreu um processo de redução fotoinduzida na superfícies do biopolímero.

We report some details of the ferrocyanide and ferricyanide complexes immobilized in chitosan. These immobilized complexes are characterized by electrochemistry, and infrared and Mössbauer spectroscopy. Alterations are observed in the infrared and Mössbauer spectra and in the cyclic voltammograms of the material prepared with ferricyanide when this material is irradiated with sunlight. These alterations indicate that the ferricyanide ion undergoes a photoinductive reduction on the biopolymeric surface.