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.