The synthesis of polystyrene or poly(methyl methacrylate) in the presence of carboxymethyl cellulose (CMC), a cellulose derivative, was carried out by emulsion polymerization using a cationic surfactant, cetyltrimethylammonium bromide (CTAB). First, the complex formation between CTAB and CMC was studied by surface tension measurements. The polymerization condition chosen was that corresponding to CMC chains fully saturated with CTAB and to the onset of pure surfactant micelle formation, namely, at 0.25 mmol L-1 CTAB and 1.0 g L-1 CMC. The hybrid particles were characterized by ζ potential and light scattering measurements and scanning electron microscopy. All dispersions were stable in the ionic strength of 2.0 mol L-1 NaCl at least for 4 days. The colloidal stability was attributed to the presence of a hydrated CMC layer around the particles. The present procedure brings the advantage of synthesizing and stabilizing particles with functional groups on the surface in a one-step method using very small amounts of surfactant, a friendly condition for the environment.

Hydrophobic films of polystyrene synthesized in bulk (PS) and by emulsion polymerization in the presence of the cationic surfactant cetyltrimethylammonium bromide (PS-CTAB) or the anionic surfactant sodium dodecyl sulfate (PS-SDS) were characterized by means of ellipsometry, contact angle measurements, and atomic force microscopy. Thin (approximately 65 nm) and thick (approximately 300 nm) films were spin-coated on hydrophilic silicon wafers. PS films presented scarcely tiny holes, while PS-CTAB and PS-SDS films presented holes and protuberances. The former were attributed to dewetting effects and the latter to surfactant clusters. The films were exposed to water or to a 0.1 mol/L NaCl solution for 24 h. Ex situ measurements evidenced strong topographic alterations after the exposure to the fluid. A model based on the diffusion of water (or electrolyte) molecules to the polymer/silcon dioxide interface through holes or defects on the film edges was proposed to explain the appearance of wrinkles and protuberances. In situ ellipsometric measurements were performed and compared with simulations, which considered either a water layer between a polymer and a silcon dioxide layer or an air layer between a polymer and water (medium). In the case of thin PS films, the ellipsometric angles evidenced a very thin (0.5-1.0 nm) air layer between water and the PS films. Upon increasing the PS film thickness, no air layer could be observed by ellipsometry. Regardless of the thickness, the ellipsometric data obtained for PS-CTAB and PS-SDS films did not indicate the presence of an air layer between them and the aqueous media. The dramatic changes in the topography of PS, PS-CTAB, and PS-SDS after immersion in salt solution were explained with proposed models. From a practical point of view, this study is particularly relevant because many hydrophobic polymers are used as substrates for biomedical purposes, where the physiological ionic strength is 0.15 mol/L NaCl.

The immobilization of Concanavalin A, (Con A), onto flat surfaces formed by ultrathin films of carboxymethylcellulose, CMC, silicon wafers or spin-coated poly(methyl methacrylate), (PMMA), was studied by ellipsometry, contact angle measurements and atomic force microscopy (AFM). The formation of Con A monolayer was only observed onto CMC films. The adsorption constant of Con A onto CMC films was determined as being (2.1+/-0.2) x 10(6) L mol(-1). After assembling Con A onto CMC surfaces, these became more hydrophobic, indicating a molecular orientation of Con A hydrophilic residues to the polysaccharide and Con A hydrophobic residues to the air. The affinity of Con A for hydroxyl rich silicon surfaces or for more hydrophobic PMMA films was very weak, evidencing that nonspecific interactions play a marginal role. For comparison, the immobilization of Con A onto hybrid particles of PMMA/CMC was investigated by means of UV-spectrophotometry. Such particles carry CMC chains attached to the surface, as evidenced by mean zeta potential value of -40 mV. The adsorption constant determined for Con A onto PMMA/CMC particles was one order of magnitude smaller than that found for Con A onto CMC films. This finding indicates that the substrate geometry might influence the molecular arrangement of sugar residues on the surface, consequently affecting the sugar-Con A interaction (cluster effect).

Hybrid particles of poly(methyl methacrylate) and carboxymethylcellulose, PMMA/CMC, were attached to atomic force microscopy cantilevers and probed against concanavalin A (ConA) films formed either on Si wafers or on CMC substrate. Regardless of the substrate, the approach curves showed different inclinations, indicating that the probe first touches a soft surface and then a hard substrate. The distance corresponding to the soft layer was estimated as 20 +/- 10 nm and was attributed to the CMC layers attached to the hybrid particles surfaces. Probing PMMA/CMC particles against ConA adsorbed onto Si wafers yielded retract curves with a sawlike pattern. The average range of adhesion forces (maximum pull-off distance) and mean adhesion force were estimated as 100 +/- 40 nm and -11 +/- 7 nN, respectively, evidencing multiple adhesions between CMC sugar residues and ConA. However, upon probing against ConA adsorbed onto CMC substrates, the mean pull-off distance and mean adhesion force were reduced to 37 +/- 18 nm and -3 +/- 1 nN, respectively, indicating that the ConA molecules immobilized onto CMC films are less available to interact with the hybrid particle than the ConA molecules adsorbed onto Si wafers. Another set of experiments, where PMMA/CMC particle probed against ConA-covered Si wafers in the presence of mannose, showed that the addition of mannose led to a considerable decrease in the mean adhesion force from -11 +/- 7 to -3 +/- 1 nN. Two hypotheses have been considered to explain the effect caused by mannose addition. The first suggested the desorption of ConA from the substrate so that the hybrid particle would probe bare Si wafer (weak adhesion). The second proposed the adsorption of mannose onto the ConA layer so that mannose layer would probe against another mannose layer, leading to low adhesion forces. In situ ellipsometry and capillary electrophoresis have been applied to check the hypotheses.

A imobilização de xiloglucanas (XG) extraídas de sementes de Hymenaea coubaril (HXG) e de Tamarindus indica (TXG) sobre lâminas de Si/SiO 2 ou lâminas modificadas com grupos amina a partir de solução aquosa na concentração de 0,5 g L -1 e em pH 3,5 foi investigada através de elipsometria e medidas de microscopia de força atômica (AFM). Os experimentos foram feitos sob condições de equilíbrio (adsorção) ou de não equilíbrio (evaporação do solvente). Sob condições de equilíbrio as cadeias de HXG e TXG não adsorvem sobre lâminas de Si/SiO 2 , indicando que os grupos SiO -na superfície não interagem com as mesmas. Camadas de TXG e HXG obtidas sobre lâminas de Si/SiO 2 por evaporação do solvente apresentaram espessuras de (2,4 ± 0,4) nm e (3,8 ± 0,9) nm, respectivamente. Cadeias de TXG e HXG adsorveram sobre lâminas modificadas com grupos amina formando filmes com (1,0 ± 0,1) nm e (1,3 ± 0,1) nm de espessura, respectivamente. Após evaporação do solvente sobre lâminas modificadas com grupos aminas, formaram-se agregados e fibrilas de TXG e HXG, os quais aumentaram os valores médios de espessura e rugosidade. Independentemente do tipo de substrato, cadeias de HXG tenderam a formar camadas mais espessas que cadeias TXG. Esta tendência foi explicada com base nas características moleculares das cadeias de HXG, como por exemplo, massa molar e tamanho de persistência maiores. As isotermas de adsorção de concanavalina A (Con A) sobre TXG e HXG adsorvidas sobre lâminas modificadas com grupos amina apresentaram valor máximo de (3,3 ± 0,3) mg m -2 . Imagens de AFM mostraram moléculas de Con A densamente empacotadas sobre as superfícies de TXG e HXG. Fibrilas e agregados foram observados somente quando as superfícies de TXG e HXG foram preparadas por evaporação do solvente. Nesta situação, as moléculas de Con A adsorveram predominantemente sobre regiões livres de fibrilas e agregados.Immobilization of xyloglucans extracted from Hymenaea coubaril (HXG) and Tamarindus indica seeds (TXG) on Si/SiO 2 wafers or amino-terminated wafers from aqueous solution at concentration of 0.5 g L -1 and pH 3.5 has been investigated by means of ellipsometry and atomic force microscopy (AFM) measurements. Experiments were carried out under equilibrium conditions (adsorption) and non-equilibrium conditions (casting). Under equilibrium conditions neither TXG nor HXG chains adsorbed from solution onto Si/SiO 2 surfaces, indicating that negatively charged SiO -groups on the surface do not attract XG chains. Casting TXG and HXG solutions onto Si/SiO 2 surfaces led to layers (2.4 ± 0.4) nm and (3.8 ± 0.9) nm thick, respectively. TXG and HXG adsorbed onto amino-terminated surfaces forming layers (1.0 ± 0.1) nm and (1.3 ± 0.1) nm thick, respectively. Upon casting solutions of TXG and HXG onto aminoterminated surfaces, aggregates and fibrils appeared more frequently on the surface, increasing the mean thickness and roughness values. Regardless the substrate, HXG chains tended to form thicker layers than TXG chains did. This trend can be explained with basis...

Chitosan (CH) decorated polystyrene (PS) particles were synthesized within complexes of CH, a polycation under acid conditions, and tiny amounts of sodium dodecylsulfate (SDS). Particle characterization was performed by means of dynamic light scattering, zeta potential measurements, and transmission electron microscopy. All dispersions were stable in the ionic strength of 2.0 mol L-1 NaCl during 2 months. The outstanding colloidal stability was attributed to the presence of a hydrated CH layer around the particles. CH decorated PS particles were attached to atomic force microscopy cantilevers and probed against Si wafers in water and in NaCl 0.01 mol/L. The mean thickness of CH layer amounted to 35 +/- 11 and 16 +/- 6 nm, when the medium was water and NaCl 0.01 mol/L, respectively. Adsorption isotherm of hexokinase (HK) onto PS/CH particles studied by means of spectrophotometry showed three regions: an initial step; adsorption plateau and multilayer formation. Enzymatic activity of free HK and immobilized HK was monitored by means of spectrophotometry as a function of storing time and reuse. After 3 days, storing HK free in solution dramatically lost its catalytic properties. On the contrary, HK-covered PS/CH particles retained enzymatic activity over 1 month. Moreover, HK-covered PS/CH particles could be reused in the determination of glucose two times consecutively, without losing activity. These interesting findings were discussed in light of the role of water in enzyme conformation.

Imobilização de proteínas sobre superfícies de polissacarídeos Errata Página 24 No 1° parágrafo, linha 5, substituir "apergillus e mucor" por Aspergillus e Mucor Página 32 No 2° parágrafo, linha 3, substituir "desacetilação" por acetilação Página 44 Figura 4a-substituir "corrente" por diferença de potencial (V) Página 45 Onde estiver escrito "corrente" leia diferença de potencial (V) Página 49 No 2° parágrafo, linha 2, substituir "como mostra a figura 7a" por como mostram as imagens de topografia (figura 7a) e de fase (figura 7c). Página 54 No 3° parágrafo, linha 5, após a referência bibliográfica, acrescentar: do que os oligômeros XXXG presentes na cadeia de TXG. Página 71 No início do 2° parágrafo, acrescentar: As curvas de força das figuras 17 a 20 apresentam em azul a aproximação do cantilever e em preto o afastamento do mesmo. Página 81 Legenda da figura 24b: A esfera verde representa PS, a linha preta quitosana, as esferas azuis moléculas de água de hidratação e as estruturas amarelas moléculas de HK. Todos os elementos estão fora de escala. Página 87 No início do 3° parágrafo, acrescentar: As curvas de força das figuras 27 a 28 apresentam em preto a aproximação do cantilever e em vermelho o afastamento do mesmo.

Ultrathin films of polysaccharides provide convenient conditions for the immobilization of biomolecules, promoting the development of biosensors supported on renewable sources [1-3]. Specific interactions such as protein-substrate, antigen-antibody and lectin-carbohydrate can be used with advantage for the creation of biotechnological devices.