Chitosan was reacted with monochloroacetic acid at room temperature for different reaction times (3h, 5h, 7h and 10h) and employing two chitosan/monochloroacetic acid molar ratios (1:4.3 or 1:8.6). The carboxymethylation of chitosan was confirmed by ¹H NMR and 13C NMR spectroscopy. The carboxymethylchitosans had average degrees of substitution ranging from 0.52 to 1.44 as determined by potentiometric and conductimetric analysis. The occurrence of N,O-carboxymethylation was also observed in all cases.

Films of chitosan and N,N,N-trimethylchitosan were cast from aqueous solutions. Chitosan was dissolved in 1% acetic acid while deionized water was the solvent for N,N,N-trimethylchitosan chloride. The resulting films presented different mechanical behaviors as evaluated by DMTA. The film of chitosan exhibited an elastic-type behavior while that of N,N,N-trimethylchitosan was typically viscous. No glass transition temperatures were observed; however, a discrete thermal transition was detected at 25 °C in the case of the N,N,N-trimethylchitosan.

A quitosana é um polissacarídeo linear obtido da desacetilação da quitina. As propriedades físico-químicas da quitosana são função do grau médio de acetilacão <img border=0 id="_x0000_i1026" src="../../../../img/revistas/po/v13n4/19880x1.gif" align=absmiddle>e da massa molar média (<img border=0 id="_x0000_i1027" src="../../../../img/revistas/po/v13n4/19880x2.gif" align=absmiddle>). Várias aplicações da quitosana foram propostas na literatura, principalmente no tratamento de águas, produção de cosméticos, drogas e medicamentos, aditivos alimentícios, membranas semipermeáveis e no desenvolvimento de biomateriais. Neste trabalho, três diferentes tipos de quitosanas comerciais foram caracterizados por ressonância magnética nuclear de hidrogênio (RMN ¹H), espectroscopia de absorção na região do infravermelho (IV), titulação condutimétrica e análise térmica (TG e DSC) com o objetivo de comparar as características de quitosanas provenientes de diferentes fornecedores. A massa molar média das amostras foi determinada a partir de medidas de viscosidade intrínseca. Os resultados obtidos por estas técnicas mostraram diferenças quanto ao grau médio de acetilação (ou desacetilação), em função da procedência do material. Os resultados obtidos da análise térmica permitiram acompanhar os processos de desidratação, decomposição e a temperatura de transição vítrea (Tg).

Chitosan is a linear polysaccharide obtained from the deacetylation of chitin. The physico-chemical properties of chitosan dependent on the average degree of acetylation (<img border=0 id="_x0000_i1029" src="../../../../img/revistas/po/v13n4/19880x8.gif" align=absmiddle>) and of the average molar mass (<img border=0 id="_x0000_i1030" src="../../../../img/revistas/po/v13n4/19880x2.gif" align=absmiddle>). Several applications of chitosan have been proposed in the literature, mainly in water treatment, cosmetic and drug manufacturing, food additives, semipermeable membranes and development of biomaterials. In this work, three commercial chitosan samples were characterized by proton nuclear magnetic resonance (¹H NMR), infrared spectroscopy (IR), conductimetric titration and thermal analysis (TG and DSC) in order to compare commercial chitosans from different supplies. The average viscosimetric molecular weight Mv was estimated from the intrinsic viscosity. The results confirmed remarkable differences in relation to the mean degree of acetylation (<img border=0 id="_x0000_i1031" src="../../../../img/revistas/po/v13n4/19880x8.gif" align=absmiddle>) (or desacetylation, <img border=0 id="_x0000_i1032" src="../../../../img/revistas/po/v13n4/19880x3.gif" align=absmiddle>). The thermal analysis data permitted to follow the dehydration, decomposition, and glass transition temperature (Tg).

In this work the formation of multilayers composed by carboxymethylcellulose (CMC), chitosane and bovine serum albumin (BSA) was studied by ellipsometry. First, the adsorption behavior of carboxymethylcellulose onto amino-terminated surfaces was investigated as a function of molecular weight and average degree of substitution of CMC. The influence of these parameters on the adsorbed amount of CMC onto amino-terminated substrates was absent. However, the interaction of CMC covered surfaces with chitosane and BSA was favored when the average degree of substitution of CMC was increased. The adsorption of BSA onto the polysaccharide systems was studied as a function of pH. At the isoelectric point of BSA a maximum in the adsorbed amount was found.

Quitosanas comercial e purificadas nas formas neutra, acetato e cloridrato foram caracterizadas e comparadas quanto a solubilidade, hidrofilicidade, morfologia de suas superfícies e cristalinidade. As amostras bruta e purificada na forma neutra apresentam características e propriedades semelhantes, mas as formas salinas, principalmente cloridratos de quitosana, são diferentes. As morfologias das superfícies da amostra comercial e das formas purificadas são semelhantes, mas cloridrato de quitosana obtido por liofilização apresenta poros que não são observados nas outras amostras. Quitosanas comercial e purificada na forma neutra não são solúveis em água, mas acetato de quitosana é parcialmente solúvel. Essas três formas de quitosana apresentam hidrofilicidades e cristalinidades semelhantes, mas nos casos dos cloridratos a presença de cargas e de contra-íons provenientes de um ácido forte aumenta a hidrofilicidade, confere hidrossolubilidade e altera significativamente as interações inter e intracadeias, modificando o empacotamento no estado sólido e resultando em importante decréscimo de cristalinidade. No caso de acetato de quitosana é observado que os cristalitos são menores, o que pode ser atribuído à protonação parcial dos grupos amino e à presença de ânions acetato.

Commercial chitosan is purified in the neutral form and as chitosan acetate and chitosan hydrochloride. These samples were characterized and compared with respect to solubility, hydrophilicity, surface's morphology and crystallinity. Commercial chitosan and its neutral purified form present similar characteristics and properties but the saline purified forms, mainly the chitosan hydrochlorides, are quite different from them. The surface morphologies of the former samples are similar but that of the lyophilized chitosan hydrochloride presents pores which are not observed in the other samples. Commercial chitosan and its neutral purified form are not soluble in pure water but chitosan acetate is partially soluble. These samples present similar hydrophylicities and crystallinities but in the cases of the chitosan hydrochlorides the presence of charges and of counter ions from a strong acid enhances the hydrophilicity, promotes solubility in water and significantly alters the interactions inter and intrachains, modifying the packing in the solid state and drastically reducing the crystallinity. In the case of chitosan acetate it is observed that the crystallites are smaller probably due to the partial protonation of amine groups and to the presence of acetate anions.

Os processos soda/antraquinona e etanol/água foram aplicados à produção de polpas de fibras e de medulas de bagaço de cana-de-açúcar. Tais polpas foram carboximetiladas em suspensão de isopropanol/água (8/1 m/m) por 4 horas a 80(0)C, empregando a relação molar 8,5/5,4/1 para ácido monocloroacético/hidróxido de sódio/celulose. Os graus médios de susbtituição dos produtos carboximetilados foram determinados por espectroscopia ¹H R.M.N. e variaram entre 0,44 e 1,27 em função da polpa empregada na derivatização. Os derivados mais substituídos foram os melhores absorventes, sugerindo que a capacidade de retenção de água desses produtos está diretamente associada a seus graus de substituição.

Two pulping methods were used on fibers and pith of sugar cane bagasse: soda/anthraquinone and ethanol/water. These pulps were submitted to carboxymethylation in a slurry of isopropanol/water (8/1 m/m) at 80ºC for 4 hours using a molar relation 8,8/5,4/1 of monochloroacetic acid/sodium hydroxyde/cellulose. The average degrees of substitution of the carboxymethylated products, determined by ¹H N.M.R. spectroscopy, were between 0.44 and 1.27, depending on the pulp employed for derivatization. The more substituted pulps were the more absorbent products, suggesting that the water retention capacity of these products is closely associated to their degrees of substitution.

Amostras de carboximetilcelulose foram preparadas por reação heterogênea de polpa soda/antraquinona obtida de fibras pré-hidrolisadas de bagaço de cana-de-açúcar. As amostras com os menores graus de substituição (<img width=32 height=32 src="http://img/revistas/po/v9n2/7939s1.gif" align=absmiddle> < 1,0) e as mais substituídas (<img width=32 height=32 src="http://img/revistas/po/v9n2/7939s1.gif" align=absmiddle>> 1,0) apresentaram comportamentos diferentes quanto a: i) variação de constante aparente de acidez (pk ap) com o grau de dissociação; ii) concordância entre os valores de <img width=32 height=32 src="http://img/revistas/po/v9n2/7939s1.gif" align=absmiddle>determinados por titulações e por espectroscopia ¹H rmn e iii) concordância entre os valores experimentais de coeficientes de transporte e os previstos pelo modelo de Manning. Todas as amostras apresentaram um padrão de substituição em blocos que, nas amostras menos substituídas são curtos e espaçados, favorecendo interações associativas que levam à agregação. Efeitos de volume excluído eletrostático, mais importantes nas amostras mais substituídas, inibem a agregação e explicam o comportamento observado nesses casos.

Samples of carboxymethylcellulose were prepared by the heterogeneous reaction of the soda/anthraquinone pulp obtained from sugar cane bagasse. The less substituted samples (DS<1,0) and the more substituted ones (DS> 1,0) showed different behaviors concerning to: i) the dependence of pk ap on the degree of neutralization; ii) the agreement between DS values determined by titrations and by ¹H nmr spectroscopy and iii) the agreement between the experimental values of transport coefficients (f) and the ones calculated by applying the Manning theoretical approach. All samples showed a block distribution of substituents which, in the case of the less substituted samples, are short and well separated, favoring the occurrence of associative interactions and of aggregation. Electrostatic excluded volume effects, which are more important for the more substituted samples, inhibit the aggregation and may explain the behavior of these samples.

RESUMO: Procedimentos adequados para as purificações de quitosana comercial como cloridrato e na forma neutralizada são descritos. As amostras obtidas apresentam elevado grau de pureza e baixo teor de cinzas conforme verificado através de termogravimetria. As determinações de graus de acetilação por espectroscopia de ressonância magnética nuclear (<img width=32 height=32 src="http://img/fbpe/po/v8n4/8292s1.gif" align=absmiddle > ou = 23,6%) e por titulações (<img width=32 height=32 src="http://img/fbpe/po/v8n4/8292s1.gif" align=absmiddle > ou = 23,0%) apresentam muito boa concordância. O cloridrato de quitosana é solúvel em água, o que permite determinações de viscosidade intrínseca em solventes aquosos na ausência de excesso de ácido e facilita a comparação de quitosana com outros polieletrólitos quanto a estimativas de rigidez/flexibilidade.

ABSTRACT: The procedures for the purification of a commercial chitosan as a hydrochloride and in the neutralized form are described. By applying these procedures, pure chitosans of low ash contents are obtained as determined by thermogravimetry. The agreement between the values of degrees of acetylation determined by conductimetric titrations (<img width=32 height=32 src="http://img/fbpe/po/v8n4/8292s4.gif" align=absmiddle > or = 23,0%) and by ¹H nmr spectroscopy (<img width=32 height=32 src="http://img/fbpe/po/v8n4/8292s4.gif" align=absmiddle > or = 23,6%) is very good. Chitosan hydrochloride being soluble in pure water allows the determination of intrinsic viscosity in dilute acid-free aqueous solutions and makes easier the comparison of chitosan and other polyelectrolytes with respect to their chain rigidity/flexibility.

RESUMO: Polpas etanol/água de medula de bagaço de cana de açúcar foram empregadas para a obtenção de carbóxi-metil-celulose insolúvel, aplicável como material absorvente. Tipicamente, a reação de carbóxi-metilação da polpa branqueada foi realizada em suspensão de isopropanol/água (1:8 / m:m) a 80 ºC por 4 horas, empregando-se relação molar 1 / 5,4 / 8,8 de celulose / NaOH / ClAcOH. O material com melhores características corresponde a um produto muito pouco solúvel (S W < 2%), com propriedades absorventes superiores às da polpa de partida.

ABSTRACT: Ethanol/water pulp of pith from sugar cane bagasse was used for the obtention of insoluble carboxymethylcellulose applicable as absorbent material. Typically the carboxymethylation reaction of the bleached pulp was carried out at 80 °C for 4 hours in isopropanol/water suspension 1:8 (w/w) employing a 1.0 / 5.4 / 8.8 cellulose / NaOH / ClAcOH molar ratio. The material with the best absorbent characteristics corresponds to a very insoluble product (S W < 2%) possessing better absorbent properties than the pulp of pith used for its obtention.