Adsorption of cationic cellulose derivative/anionic surfactant complexes onto solid surfaces. II. Hydrophobized silica surfaces

The effect of the anionic surfactant SDS (sodium dodecyl sulfate) on the adsorption behavior of cationic hydroxyethyl cellulose (Polymer JR-400) and hydrophobically modified cationic cellulose (Quatrisoft LM-200) at hydrophobized silica has been investigated by null ellipsometry and compared with the previous data for adsorption onto hydrophilic silica surfaces. The adsorbed amount of LM-200 is found to be considerably larger than the adsorbed amount of JR-400 at both surfaces. Both polymers had higher affinity toward hydrophobized silica than to silica. The effect of SDS on polymer adsorption was studied under two different conditions: adsorption of polymer/SDS complexes from premixed solutions and addition of SDS to preadsorbed polymer layers. Association of the surfactant to the polymer seems to control the interfacial behavior, which depends on the surfactant concentration. For the JR-400/SDS complex, the adsorbed amount on hydrophobized silica started to increase progressively from much lower SDS concentrations, while the adsorbed amount on silica increased sharply only slightly below the phase separation region. For the LM-200/SDS complex, the adsorbed amounts increased progressively from very low SDS concentrations at both surfaces, and no large difference in the adsorption behavior was observed between two surfaces below the phase separation region. The complex desorbed from the surface at high SDS concentrations above the critical micelle concentration. The reversibility of the adsorption of polymer/SDS complexes upon rinsing was also investigated. When the premixed polymer/SDS solutions at high SDS concentrations (>5 mM) were diluted by adding water, the adsorbed amount increased due to the precipitation of the complex. The effect of the rinsing process on the adsorbed layer was determined by the hydrophobicity of the polymer and the surface.     

The salivary mucin MUC5B and lactoperoxidase can be used for layer-by-layer film formation

In situ ellipsometry was used to study layer-by-layer film formation on hydrophilic and hydrophobized silica surfaces by alternating sequential adsorption of human mucin MUC5B and cationic proteins lysozyme, lactoferrin, lactoperoxidase or histatin 5, respectively. The stability of the multilayers was investigated by addition of sodium dodecyl sulfate solution (SDS). Atomic force microscopy was employed to investigate morphological structures on the surfaces during the layer-by-layer film build-up. It was clearly shown that, on both hydrophilic and hydrophobized silica, only MUC5B and lactoperoxidase showed the ability for multilayer formation, resulting in an approximately linear increase in adsorbed amount and film thickness with each deposition cycle. The net increase in amounts per cycle was larger on the hydrophilic silica. Further, MUC5B needs to be adsorbed first on the hydrophilic substrates to obtain this fast build-up behavior. Generally, addition of SDS solution showed that a large fraction of the adsorbed film could be desorbed. However, films on the hydrophobized silica were more resistant to surfactant elution. In conclusion, MUC5B-cationic protein multilayers can be formed on hydrophilic and hydrophobized silica, depending on the choice of the cationic protein as well as in which order the build-up is started on hydrophilic silica. Additionally, SDS disrupts the layer-by-layer film formed by MUC5B and lactoperoxidase.     

Studies on the exchange of early pellicle proteins by mucin and whole saliva

Adsorption of small pellicle proteins statherin or proline-rich protein 1 (PRP1), respectively, and subsequent adsorption of human whole saliva (HWS) or salivary mucin MUC5B, respectively, was studied using ellipsometry and total internal reflectance fluorescence. Differences in elution (using sodium dodecyl sulphate (SDS) solutions) between mixed and single protein films were also investigated. On both hydrophilic and hydrophobized surfaces HWS and MUC5B were found to adsorb to pre-adsorbed layers of statherin and PRP1, respectively. Statherin adsorption on both substrate types showed no or minor exchange by HWS or MUC5B and no change in SDS elution between mixed and single protein films. Small amounts of PRP1 were exchanged by HWS on both surface types and the SDS elutable fractions were similar or larger for mixed films compared to single protein films. PRP1 and MUC5B in sequence showed minor exchange of PRP1 on hydrophilic surfaces, while no exchange could be established on hydrophobized substrates. SDS elutable fractions decreased for PRP1 and MUC5B mixed films compared to single protein films. In conclusion, minor amounts of statherin and PRP1 are exchanged during the time course of the experiments, which indicates that these proteins may to a large extent remain incorporated in the pellicle.     

Adsorption behaviour and surfactant elution of cationic salivary proteins at solid/liquid interfaces,studied by in situ ellipsometry

Adsorption of the cationic salivary proteins lactoferrin, lactoperoxidase, lysozyme and histatin 5 to pure (hydrophilic) and methylated (hydrophobized) silica surfaces was investigated by in situ ellipsometry. Effects of concentration (≤10 μg ml⁻¹, for lysozyme ≤200 μg ml⁻¹) and dependence of surface wettability, as well as adsorption kinetics and elutability of adsorbed films by buffer and sodium dodecyl sulphate (SDS) solutions were investigated. Results showed that the amounts adsorbed decreased in the order lactoferrin ≥ lactoperoxidase > lysozyme ≥ histatin 5. On hydrophilic silica, the adsorption was most likely driven by electrostatic interactions, which resulted in adsorbed amounts of lactoferrin that indicated the formation of a monolayer with both side-on and end-on adsorbed molecules. For lactoperoxidase the adsorbed amounts were somewhat higher than an end-on monolayer, lysozyme adsorption showed amounts corresponding to a side-on monolayer, and histatin 5 displayed adsorbed amounts in the range of a side-on monolayer. On hydrophobized substrata, the adsorption was also mediated by hydrophobic interactions, which resulted in lower adsorbed amounts of lactoferrin and lactoperoxidase; closer to side-on monolayer coverage. For both lysozyme and histatin 5 the adsorbed amounts were the same as on the hydrophilic silica. The investigated proteins exhibited fast adsorption kinetics, and the initial kinetics indicated mass transport controlled behaviour at low concentrations on both types of substrates. Buffer rinsing and SDS elution indicated that the proteins in general were more tightly bound to the hydrophobized surface compared to hydrophilic silica. Overall, the surface activity of the investigated proteins implicates their importance in the salivary film formation.     

Adsorption of trypsin on hydrophilic and hydrophobic surfaces

The adsorption of trypsin onto polystyrene and silica surfaces was investigated by reflectometry, spectroscopic methods, and atomic force microscopy (AFM). The affinity of trypsin for the hydrophobic polystyrene surface was higher than that for the hydrophilic silica surface, but steady-state adsorbed amounts were about the same at both surfaces. The conformational characteristics of trypsin immobilized on silica and polystyrene nanospheres were analyzed in situ by circular dichroism and fluorescence spectroscopy. Upon adsorption the trypsin molecules underwent structural changes at the secondary and tertiary level, although the nature of the structural alterations was different for silica and polystyrene surfaces. AFM imaging of trypsin adsorbed on silica showed clustering of enzyme molecules. Rinsing the silica surface resulted in 20% desorption of the originally adsorbed enzyme molecules. Adsorption of trypsin on the surface of polystyrene was almost irreversible with respect to dilution. After adsorption on silica the enzymatic activity of trypsin was 10 times lower, and adsorbed on polystyrene the activity was completely suppressed. The trypsin molecules that were desorbed from the sorbent surfaces by dilution with buffer regained full enzymatic activity.     

A comparative study of surfactant adsorption on model surfaces using the quartz crystal microbalance and the ellipsometer

The nature of hexaethylene glycol mono-n-tetradecyl ether (C(14)EO(6)) layers adsorbed onto different model surfaces was systematically investigated by means of QCM-D (quartz crystal microbalance-dissipation) and ellipsometry. The amount of non-ionic surfactant adsorbed is determined both at hydrophilic and hydrophobic surfaces. In particular, the substrates employed were hydrophilic silica, hydrophobized silica (using dimethyldichlorosilane), and hydrophobized gold surfaces (using 10-thiodecane and 16-thiohexadecane). It was shown that the frequency shift obtained from the QCM-D experiments results in an overestimation of the adsorbed mass. This is attributed to two different effects, viz. water that is coupled to the adsorbed layer due to hydration of the polar region of the surfactant and second water that for other reasons is trapped within the adsorbed layer. Furthermore, from the ellipsometry data the adsorbed layer thickness is determined. By combining the thickness information and the dissipation parameter (obtained from the QCM-D experiments), we note that the dissipation parameter is insufficient in describing the viscoelastic character of thin surfactant films.     

Modifying the adsorption properties of anionic surfactants onto hydrophilic silica using the pH dependence of the polyelectrolytes PEI, ethoxylated PEI, and polyamines

The manipulation of the adsorption of the anionic surfactant, sodium dodecyl sulfate, SDS, onto hydrophilic silica by the polyelectrolytes, polyethyleneimine, PEI, ethoxylated PEI, and the polyamine, pentaethylenehexamine, has been studied using neutron reflectometry. The adsorption of a thin PEI layer onto hydrophilic silica promotes a strong reversible adsorption of the SDS through surface charge reversal induced by the PEI at pH 7. At pH 2.4, a much thicker adsorbed PEI layer is partially swelled by the SDS, and the SDS adsorption is now no longer completely reversible. At pH 10, there is some penetration of SDS and solvent into a thin PEI layer, and the SDS adsorption is again not fully reversible. Ethoxylation of the PEI (PEI-EO(1) and PEI-EO(7)) results in a much weaker and fragile PEI and SDS adsorption at both pH 3 and pH 10, and both polymer and surfactant desorb at higher surfactant concentrations (>critical micellar concentration, cmc). For the polyamine, pentaethylenehexamine, adsorption of a layer of intermediate thickness is observed at pH 10, but at pH 3, no polyamine adsorption is evident; and at both pH 3 and pH 10, no SDS adsorption is observed. The results presented here show that, for the amine-based polyelectrolytes, polymer architecture, molecular weight, and pH can be used to manipulate the surface affinity for anionic surfactant (SDS) adsorption onto polyelectrolyte-coated hydrophilic silica surfaces.     

Concomitant adsorption of poly(ethylene oxide)-b-poly(epsilon-caprolactone) copolymers and sodium dodecyl sulfate at the silica-water interface

Upon addition of silica to aqueous solutions of poly(ethylene oxide)-b-poly(epsilon-caprolactone) copolymers (PEO-b-PCL) and sodium dodecyl sulfate (SDS), adsorption of the solutes occurs at the silica-water interface. The amount of the adsorbed constituents has been measured by the total concentration depletion method. Small-angle neutron scattering experiments (SANS) have been carried out to investigate the structure of the adsorbed layer. Although SDS is not spontaneously adsorbed onto hydrophilic silica, adsorption is observed in the presence of PEO-b-PCL diblocks, in relation to the relative concentration of the two compounds. Conversely, SDS has a depressive effect on the adsorption of the copolymer, whose structure at the interface is modified. Copolymer desorption is however never complete at high SDS content. These observations have been rationalized by the associative behavior of PEO-b-PCL and SDS in water.     

Adsorption of copolymers aggregates: from kinetics to adsorbed layer structure

We examined the adsorption, on hydrophobic and hydrophilic surfaces, of 4 rake-type poly(dimethyl siloxane) (PDMS) copolymers varying the amount of poly(ethylene glycol) (PEG) graft arms from 41 to 72%. The copolymers formed large aggregates in solution, complicating their adsorption kinetics and layer structures. We found the adsorption process always to be dominated by the adsorption of large aggregates, with strongly bound layers resistant to rinsing in adsorbing buffer. Adsorbed amounts were nearly independent of the substrate. However, subtleties in the adsorption kinetics suggested different layer structures for the different systems. On hydrophilic silica, aggregates adsorbed at the transport limited rate until surface saturation, and associated interfacial structures were likely retained. On the hydrophobic surface, a subset of the copolymers exhibited retarded late stage adsorption kinetics suggestive of brush formation. This work demonstrates how subtle differences in adsorption kinetics provide insight into potential interfacial layer structures.     

Adsorption of a statherin peptide fragment on the surface of nanocrystallites of hydroxyapatite

Statherin is an active inhibitor of calcium phosphate precipitation in the oral cavity. For many studies of the interaction between statherin and hydroxyapatite (HAp), the samples are prepared by a direct mixing of statherin or its fragment with well-crystalline HAp crystals. In this work, the HAp sample is precipitated in the presence of peptide fragment derived from the N-terminal 15 amino acids of statherin (SN-15). The in situ prepared HAp crystallites are nanosized, leading to a significant increase of the peptide amount adsorbed on the HAp surface. The enhancement in NMR sensitivity allows, for the first time, the measurement of a two-dimensional 13C-13C correlation spectrum for a 13C uniformly labeled peptide sample adsorbed on mineral surface. The measurement time is about 18.5 h at a field strength of 7.05 T. Preliminary results suggest that there may exist two different mechanisms for the interaction between SN-15 and HAp. In addition to the one which will cause a conformational change near the N-terminal, SN-15 may also be absorbed on the HAp surface by simple electrostatic interaction, without any significant conformational changes of the peptides.     

Manipulation of the adsorption of ionic surfactants onto hydrophilic silica using polyelectrolytes

This paper demonstrates the use of polyelectrolytes to modify and manipulate the adsorption of ionic surfactants onto the hydrophilic surface of silica. We have demonstrated that the cationic polyelectrolyte poly(dimethyl diallylammonium chloride), poly-dmdaac, modifies the adsorption of cationic and anionic surfactants to the hydrophilic surface of silica. A thin robust polymer layer is adsorbed from a dilute polymer/surfactant solution. The resulting surface layer is cationic and changes the relative affinity of the cationic surfactant hexadecyl trimethylammonium bromide, C16TAB, and the anionic surfactant sodium dodecyl sulfate, SDS, to adsorb. The adsorption of C16TAB is dramatically reduced. In contrast, strong adsorption of SDS was observed, in situations where SDS would normally have a low affinity for the surface of silica. We have further shown that subsequent adsorption of the anionic polyelectrolyte sodium poly(styrene sulfonate), Na-PSS, onto the poly-dmdaac coated surface results in a change back to an anionic surface and a further change in the relative affinities of the cationic and anionic surfactants for the surface. The relative amounts of C16TAB and SDS adsorption depend on the coverage of the polyelectrolyte, and these preliminary measurements show that this can be manipulated.     

Spreading of proteins and its effect on adsorption and desorption kinetics

The kinetics of adsorption of lysozyme and alpha-lactalbumin from aqueous solution on silica and hydrophobized silica has been studied. The initial rate of adsorption of lysozyme at the hydrophilic surface is comparable with the limiting flux. For lysozyme at the hydrophobic surface and alpha-lactalbumin on both surfaces, the rate of adsorption is lower than the limiting flux, but the adsorption proceeds cooperatively, as manifested by an increase in the adsorption rate after the first protein molecules are adsorbed. At the hydrophilic surface, adsorption saturation (reflected in a steady-state value of the adsorbed amount) of both proteins strongly depends on the rate of adsorption, but for the hydrophobic surface no such dependency is observed. It points to structural relaxation ("spreading") of the adsorbed protein molecules, which occurs at the hydrophobic surface faster than at the hydrophilic one. For lysozyme, desorption has been studied as well. It is found that the desorbable fraction decreases after longer residence time of the protein at the interface.     

Adsorption of anionic and cationic surfactants on anionic colloids: supercharging and destabilization

We present herein a study on the adsorption of anionic (SDS), cationic (CTAB), and nonionic (C(12)E(5)) surfactants onto anionic silica nanoparticles. The effects of this adsorption are studied by means of the static structure factor, S(q), and the collective diffusion coefficient, D(c), obtained from small-angle X-ray scattering and dynamic light scattering measurements, respectively. The effective charge on the particles was determined also from classical electrophoresis and electroacoustic sonic-amplitude measurements. The surface tension of the sample was also investigated. Of particular note is the adsorption of SDS onto the silica nanoparticles, which leads to supercharging of the interface. This has interesting repercussions for structures obtained by the layer-by-layer (LbL) technique, because emulsions stabilized with supercharged and hydrophobized silica are perfect candidates for use in a multilayer system.     

In situ adsorption studies of a 14-amino acid leucine-lysine peptide onto hydrophobic polystyrene and hydrophilic silica surfaces using quartz crystal microbalance, atomic force microscopy, and sum frequency generation vibrational spectroscopy

The adsorption of a 14-amino acid amphiphilic peptide, LK14, which is composed of leucine (L, nonpolar) and lysine (K, charged), on hydrophobic polystyrene (PS) and hydrophilic silica (SiO2) was investigated in situ by quartz crystal microbalance (QCM), atomic force microscopy (AFM), and sum frequency generation (SFG) vibrational spectroscopy. The LK14 peptide, adsorbed from a pH 7.4 phosphate-buffered saline (PBS) solution, displayed very different coverage, surface roughness and friction, topography, and surface-induced orientation when adsorbed onto PS versus SiO2 surfaces. Real-time QCM adsorption data revealed that the peptide adsorbed onto hydrophobic PS through a fast (t < 2 min) process, while a much slower (t > 30 min) multistep adsorption and rearrangement occurred on the hydrophilic SiO2. AFM measurements showed different surface morphologies and friction coefficients for LK14 adsorbed on the two surfaces. Surface-specific SFG spectra indicate very different ordering of the adsorbed peptide on hydrophobic PS as compared to hydrophilic SiO2. At the LK14 solution/PS interface, CH resonances corresponding to the hydrophobic leucine side chains are evident. Conversely, only NH modes are observed at the peptide solution/SiO2 interface, indicating a different average molecular orientation on this hydrophilic surface. The surface-dependent difference in the molecular-scale peptide interaction at the solution/hydrophobic solid versus solution/hydrophilic solid interfaces (measured by SFG) is manifested as significantly different macromolecular-level adsorption properties on the two surfaces (determined via AFM and QCM experiments).     

Silica supported phospholipid layers doped with GM1: A comparison between different methods

A method to coat hydrophobic surfaces with lipid molecules in a reproducible manner and in which the lipid molecules are resistant to detergent washings, would benefit the development of new ELISA assays. This work presents different approaches to build 1,2-dioleolyl-sn-glycero-3-phosphocholine (DOPC) layers doped with a monosialoganglioside (GM1) supported on silica surfaces, which are stable toward buffer rinsing and washing with surfactant (Tween 20). The three methods employed were: method 1, coadsorption of DOPC:GM1 (0-10 mol%) with the surfactant n-dodecyl-beta-D-maltoside (DDM) from micellar solutions, with successive adsorption and rinsing steps; method 2, vesicle fusion from DOPC: GM1 (0-10 mol%) liposomes; and method 3, deposition of GM1 from organic solvent (chloroform) and exposure to an aqueous environment (hydration method). The vesicle fusion method was also tested in polystyrene surfaces. Cholera toxin subunit B (CTB) was used to detect the presence of GM1 on the formed layers. The results indicated that the vesicle fusion was the only method that was successful in creating stable mono- and bilayers onto hydrophobized and hydrophilic silica, respectively. The mixed micellar solution method was suitable for creating pure lipid (DOPC) monolayers but the incorporation of GM1 in the micelles led to monolayers which were very unstable with respect to buffer rinsing. The hydration method led to monolayers of GM1 that were partly rinsed off by a continuous buffer flow. Adsorption of CTB was found to be proportional to the amount of GM1 present in the liposomes. The amount of CTB adsorbed onto the lipid bilayers was roughly the double as the one determined on the monolayers with the same liposome compositions. The vesicle fusion method was also able to create monolayers of pure DOPC and DOPC:10 mol% GM1 on the polystyrene surfaces.     

Layer-by-layer assembly of mucin and chitosan--Influence of surface properties, concentration and type of mucin

Bovine submaxillary mucin (BSM) and chitosan were used to build layer-by-layer structures on solid substrates. The build-up was monitored using in situ ellipsometry to obtain time resolved values of the thickness and adsorbed amount. Additionally surface morphology during build-up was studied by atomic force microscopy (AFM). It was found that the adsorbed amount of the film increases approximately linearly with each deposition cycle on hydrophobized silica whereas construction on silica was found not to be possible at the experimental conditions used. We conclude that sufficient amount of the first mucin layer is crucial for the subsequent multilayer formation. The complex build-up kinetics on hydrophobized silica is characterized by adsorption and redissolution processes and the overall growth is the sum of both processes. AFM imaging on hydrophobized silica also confirmed the presence of redissolution processes and chitosan addition led to a reduction both in the number of surface aggregates and in the roughness of the surface. The present work also shows that by adjusting the relative concentrations of the polyelectrolytes it is possible to change the growth rate considerably. The final structures after deposition of 8 bilayers were found to have a high content of water and film stability test revealed that a substantial amount dissolves when increasing electrolyte concentration or pH of the ambient solution. Human mucin from saliva (MUC5B) was also used to create multilayers with chitosan on hydrophobized silica and it was revealed that no redissolution appears to be present in this system.     

Analytical investigation of the self-desorption of the oligomers of mixtures of a polydisperse ethoxylated surfactant with sodium dodecylsulfate from a silica/water interface

The adsorption isotherms onto a hydrophilic silica of mixtures of sodium dodecylsulfate (SDS) and of all the oligomers of a polydisperse nonylethylene glycol n-dodecyl ether (C(12)E(9)) surfactant were determined using a high-performance liquid chromatography (HPLC) technique. Incorporation of the anionic surfactant to the negatively charged silica surface is favored by the adsorption of the nonionic surfactant. Comparison between the adsorption isotherms of mixtures of SDS with a monodisperse C(12)E(9) and a polydisperse C(12)E(9) shows that the adsorption of SDS at the silica/water interface is stronger with the latter material than with the former in a large surface coverage domain. The composition of the surface aggregates and the variation of the oligomer distribution in these aggregates were determined. The previously described phenomena called self-desorption which was observed for the global C(12)E(9) and SDS surfactant mixtures was confirmed: increasing the total concentration at a fixed surfactant ratio induces at high concentration a desorption of the anionic surfactant and all of the less polar oligomers from the solid/water interface. An interpretation scheme is proposed which assumes that the interaction of SDS is larger with the less polar oligomers than with the polar ones. The self-desorption effect could then be considered as the consequence of the polydispersity of the nonionic surfactant and to the net repulsion interaction between SDS and the silica surface as the mole fraction of SDS in the surfactant mixture increases.     

Differences between tethered polyelectrolyte chains on bare mica and hydrophobically modified mica

This study investigates the structures of layers of amphiphilic diblock copolymers of poly(t-butyl styrene)-poly(styrene sulfonate) (PtBS-PSS) adsorbed on both the bare mica surface (hydrophilic) and an octadecyltriethoxysilane (OTE)-modified mica surface (hydrophobic). When the surface is rendered hydrophobic, the nonsoluble block exhibits stronger interaction with the surface and higher adsorbed masses are achieved. Interaction forces between two such adsorbed layers on both substrates were measured using the surface forces apparatus. The effect of salt concentration (Cs) and molecular weight (N) on the height of the self-assembled layers (L0) was examined in each case. The resulting scaling relationship is in good agreement with predictions of the brush model, L0 proportional to N(1.0) in the low-salt limit and L0N(-1) proportional to (Cs/sigma)(-0.32) in the salted regime, when adsorption takes place onto the hydrophobized mica surface. For adsorption on the bare mica surface, L0N(-0.7) proportional, variant Cs(-0.17) agrees with the scaling prediction of the sparse tethering model. The results suggest that, on the hydrophilic bare mica surface, the adsorbed amount is not high enough to form a brush structure and only very little intermolecular stretching of the tethered chains occurs; in contrast, the presence of the hydrophobic OTE layer increases the tethering density such that the polyelectrolyte chains adopt a brush conformation.     

Interactions between chitosan and SDS at a low-charged silica substrate compared to interactions in the bulk--the effect of ionic strength

The effect of ionic strength on association between the cationic polysaccharide chitosan and the anionic surfactant sodium dodecyl sulfate, SDS, has been studied in bulk solution and at the solid/liquid interface. Bulk association was probed by turbidity, electrophoretic mobility, and surface tension measurements. The critical aggregation concentration, cac, and the saturation binding of surfactants were estimated from surface tension data. The number of associated SDS molecules per chitosan segment exceeded one at both salt concentrations. As a result, a net charge reversal of the polymer-surfactant complexes was observed, between 1.0 and 1.5 mM SDS, independent of ionic strength. Phase separation occurs in the SDS concentration region where low charge density complexes form, whereas at high surfactant concentrations (up to several multiples of cmc SDS) soluble aggregates are formed. Ellipsometry and QCM-D were employed to follow adsorption of chitosan onto low-charged silica substrates, and the interactions between SDS and preadsorbed chitosan layers. A thin (0.5 nm) and rigid chitosan layer was formed when adsorbed from a 0.1 mM NaNO3 solution, whereas thicker (2 nm) chitosan layers with higher dissipation/unit mass were formed from solutions at and above 30 mM NaNO3. The fraction of solvent in the chitosan layers was high independent of the layer thickness and rigidity and ionic strength. In 30 mM NaNO3 solution, addition of SDS induced a collapse at low concentrations, while at higher SDS concentrations the viscoelastic character of the layer was recovered. Maximum adsorbed mass (chitosan + SDS) was reached at 0.8 times the cmc of SDS, after which surfactant-induced polymer desorption occurred. In 0.1 mM NaNO3, the initial collapse was negligible and further addition of surfactant lead to the formation of a nonrigid, viscoelastic polymer layer until desorption began above a surfactant concentration of 0.4 times the cmc of SDS.