Mechanisms of ethyl(hydroxyethyl) cellulose-solid interaction: influence of hydrophobic modification

Hydroxyethyl cellulose and its hydrophobically modified derivatives are widely used in many industrial areas such as pharmaceuticals, cosmetics, textiles, paint and mineral industries. However, the interaction mechanisms of these biopolymers and solids have not been established. In this work, the interaction mechanism and conformation of hydrophobically modified ethyl(hydroxyethyl) cellulose (C(14)-EHEC) have been investigated using spectroscopic, AFM and allied techniques. Comparison was made with corresponding unmodified analogue in order to investigate the effects of the hydrophobic modification. Electrokinetic studies showed that polysaccharides adsorption decreased the negative zeta potential of talc but did not reverse the charge. EHEC adsorption on talc was not found to be affected significantly by changes in solution conditions such as pH and ionic strength, ruling out electrostatic force as the controlling factor. However, HM-EHEC adsorption was found to increase markedly with increase in ionic strength from 0.1 to 1 suggesting a role for the hydrophobic force in this adsorption process. Fluorescence spectroscopic studies conducted to investigate the role of hydrophobic bonding using pyrene probe showed no evidence of the formation of hydrophobic domains at talc-aqueous interface. Urea, a hydrogen bond breaker, reduced the adsorption of HM-EHEC on talc markedly. In FTIR study, the changes in the infrared bands, associated with the CO stretch coupled to the CC stretch and OH deformation, were significant and therefore support strong hydrogen bonding of HM-EHEC on the solid surface. Moreover, Langmuir modeling of the adsorption isotherms suggests hydrogen bonding to be a major force for the adsorption of EHEC and C(14)-EHEC on solid since the adsorption free energies of these polymers were close to that for hydrogen bond formation. All of the above results suggest that the main driving force for EHEC adsorption on talc is hydrogen bonding rather than electrostatic interaction or hydrophobic force. For hydrophobically modified C(14)-EHEC, hydrophobic force plays a synergetic role in adsorption along with hydrogen bonding. From computer modeling and AFM imaging, it is proposed that C(0)-EHEC and C(14)-EHEC adsorb flat on talc with ethylene oxide side chains and hydrophobic groups protruding out from the surface into bulk water phase.     

Study of galactomannose interaction with solids using AFM, IR and allied techniques

Guar gum (GG) and locust bean gum (LBG) are two galactomannose polysaccharides with different mannose/galactose ratio which is widely used in many industrial sectors including food, textiles, paper, adhesive, paint, pharmaceuticals, cosmetics and mineral processing. They are natural nonionic polymers that are non-toxic and biodegradable. These properties make them ideal for industrial applications. However, a general lack of understanding of the interactions between the polysaccharides and solid surfaces has hindered wider application of these polymers. In this work, adsorption of locust bean gum and guar gum at the solid-liquid interface was investigated using adsorption tests, electrophoretic mobility measurements, FTIR, fluorescence spectroscopy, AFM and molecular modeling. Electrokinetic studies showed that the adsorption of GG and LBG on talc do not change its isoelectric point. In addition, GG and LBG adsorption on talc was found not to be affected by changes in solution conditions such as pH and ionic strength, which suggests a minor role of electrostatic force in adsorption. On the other hand, fluorescence spectroscopy studies conducted to investigate the role of hydrophobic bonding using pyrene probe showed no evidence of the formation of hydrophobic domains at talc-aqueous interface. Moreover, urea, a hydrogen bond breaker, markedly reduced the adsorption of LBG and GG on talc, supporting hydrogen bonding as an important role. In FTIR study, the changes in the infrared bands, associated with the CO stretch coupled to the CC stretch and OH deformation, were significant and therefore also supporting hydrogen bonding of GG and LBG to the solid surface. In addition, Langmuir modeling of adsorption isotherm further suggested that hydrogen bonding is the dominant force for polysaccharide adsorption since the adsorption free energy of these polymers is close to that for hydrogen bond formation. From molecular modeling, different helical structures are observed for LBG and GG because of their different galactose/mannose ratio and these polymers were found to adsorb flat on solid to let more of its OH groups in contact with the surface. All of the above results suggest that the main driving force for adsorption both of GG and LBG on talc is hydrogen bonding rather than hydrophobic force even though there is difference in G/M ratio between them.     

In situ particle film ATR FTIR spectroscopy of carboxymethyl cellulose adsorption on talc: binding mechanism, pH effects, and adsorption kinetics

Carboxymethyl cellulose (CMC), in solution and adsorbed on the surface of talc, has been studied with ATR FTIR spectroscopy as a function of the solution pH. The solution spectra enable the calculation of the extent of ionization of the polymer (due to protonation and deprotonation of the carboxyl group) at various pH values, yielding a value of 3.50 for the pK(app)(1/2) (pH at which half of all carboxyl groups are ionized) in a simple electrolyte solution and a value of 3.37 for the pK(app)(1/2) in solutions containing magnesium ions (3.33 x 10(-4) M). The spectra of the adsorbed layer reveal that CMC interacts with the talc surface through a chemical complexation mechanism, via the carboxyl groups substituted on the polymer backbone. The binding mechanism is active at all pH values down to pH 2 and up to pH 11. The adsorbed layer spectra reveal that protonation and deprotonation of the polymer are affected by adsorption, with an increase in the pK(app)(1/2) to a value of 4.80. Spectra of the adsorbed polymer were also acquired as a function of the adsorption time. Adsorption kinetic data reveal that the polymer most likely has two different interactions with the talc surface, with a stronger interaction with the talc edge through chemical complexation and a weaker interaction with the talc basal plane presumably through the hydrophobic interaction.     

Estimation of polymer-surface interfacial interaction strength by a contact AFM technique

Atomic force microscopy (AFM) measurements were employed to assess polymer-surface interfacial interaction strength. The main feature of the measurement is the use of contact-mode AFM as a tool to scratch off the polymer monolayer adsorbed on the solid surface. Tapping-mode AFM was used to determine the depth of the scraped recess. Independent determination of the layer thickness obtained from optical phase interference microscopy (OPIM) confirmed the depth of the AFM scratch. The force required for the complete removal of the polymer layer with no apparent damage to the substrate surface was determined. Polypropylene (PP), low-density polyethylene (PE), and PP-grafted-maleic anhydride (PP-g-ma) were scraped off silane-treated glass slabs, and the strength of surface interaction of the polymer layer was determined. In all cases it was determined that the magnitude of surface interaction force is of the order of van der Waals (VDW) interactions. The interaction strength is influenced either by polymer ability to wet the surface (hydrophobic or hydrophilic interactions) or by hydrogen bonding between the polymer and the surface treatment.     

Spectroscopic investigation of the adsorption mechanisms of polyacrylamide polymers onto iron oxide particles

The mechanisms of high-molecular-weight polyacrylamide nonionic homopolymer and 25 mol% anionic acrylate-substituted copolymer adsorption onto iron oxide particles were investigated via DRIFT and UV-vis spectroscopies at three pH values (6, 8.5, and 11). While electrostatic interactions play an important role in charged polymer adsorption, this information is not spectroscopically available. At pH values above and below pH 8.5 (the isoelectric point for the anionic polymer), bidentate chelation and hydrogen bonding were the main adsorption mechanisms. At the isoelectric point, monodentate chelation was observed to be the main mode of adsorption, along with hydrogen bonding. For the nonionic polymer, in all cases, hydrogen bonding through the carbonyl group was the main mode of adsorption. The adsorption of both polymers conformed well to the Freundlich model, suggesting that the adsorbed polymer amount increases with increasing polymer concentration up to 7500 g/t solid, rather than approaching monolayer coverage. Spectroscopic evidence was found to suggest that hydrolysis of nonionic polyacrylamide occurs at high pH.     

Analysis of adsorption and binding behaviors of silver nanoparticles onto a pyridyl-terminated surface using XPS and AFM

In this study, we analyzed adsorption and binding behaviors of citrate-capped silver nanoparticles (AgNPs) on a pyridyl-terminated surface using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Adsorption of the AgNPs onto the pyridyl-terminated silicon wafer surface was completed through pH-controlled sol immersion. The adsorption occurred predominantly at a pH less than the pK(b) value of the pyridyl group and more than the pK(a1) of citric acid, indicating that the driving force behind adsorption was electrostatic interaction. Adsorption of citrate onto the pyridyl group also occurred at pK(a1) < pH < pK(b) without AgNPs. According to XPS in the N1s region, larger deprotonation from the pyridinium-formed pyridyl groups was demonstrated subsequent to adsorption of the AgNPs. The deprotonation from the pyridinium indicates the formation of the neutral pyridyl group as the counterpart of hydrogen bonding with the carboxyl group of citrate. The binding state between the pyridyl group and citrate surrounding AgNPs is expected to be kept stable through hydrogen bonding and van der Waals force derived from the AgNPs approach to the pyridyl surface.     

Binding the tobacco mosaic virus to inorganic surfaces

We studied the adsorption behavior and surface chemistry of the tobacco mosaic virus (TMV) on well-defined metal and insulator surfaces. TMV serves as a tubular supramolecular model system with precisely known surface termination. We show that if the surface chemistry of the substrate and the pH-dependent chemistry of the molecular surface match, for example, by hydrogen bonding, a strong adsorption occurs, and lateral movement is impeded. Due to the immobilization, the virion can be imaged by atomic force microscopy (AFM) in contact mode. We also used self-assembled monolayers with an acyl chloride group to induce covalent bonding via ester formation. Noncontact AFM proved that TMV keeps its cylindrical cross section only under weak adsorption conditions, that is, on hydrophobic surfaces, while on hydrophilic substrates a deformation occurs to maximize the number of interacting chemical groups.     

Mixed adsorption of poly(vinylpyrrolidone) and sodium dodecylbenzenesulfonate on kaolinite

The mixed adsorption of the nonionic polymer poly(vinylpyrrolidone) (PVP) and the anionic surfactant sodium dodecylbenzenesulfonate (SDBS) on kaolinite has been studied. Both components adsorb from their mixture onto the clay mineral. The overall adsorption process is sensitive to the pH, the electrolyte concentration, and the amounts of polymer and surfactant. Interpretation of the experimental data addresses also the patchwise heterogeneous nature of the clay surface. In the absence of PVP, SDBS adsorbs on kaolinite by electrostatic and hydrophobic interactions. However, when PVP is present, surfactant adsorption at 10(-2) M NaCl is mainly driven by charge compensation of the edges. The adsorption of PVP from the mixture shows similar behavior under different conditions. Three regions can be distinguished based on the changing charge of polymer-surfactant complexes in solutions with increasing SDBS concentration. At low surfactant content, PVP adsorbs by hydrogen bonding and hydrophobic interactions, whereas electrostatic interactions dominate at higher surfactant concentrations. Over the entire surfactant concentration range, polymer-surfactant aggregates are present at the edges. The composition of these surface complexes differs from that in solution and is controlled by the surface charge.     

Role of Surface Molecular Architecture and Energetics of Hydrogen Bonding Sites in Adsorption of Polymers and Surfactants

Hydrogen bonding is generally thought to be an ubiquitous adsorption mechanism, which often foils selective adsorption schemes. Through investigation of hydrogen bonding energy and its dependence on surface molecular architecture, it may be possible to develop new methodologies to control the adsorption of surfactants and polymeric flocculants, depressants, and dispersants used in particulate processing industries. A model system using St?ber silica spheres and polyethylene oxide, a polymer known for its ability to form hydrogen bonds, was examined. The effect of two different surface treatments of the silica particles, calcination and rehydroxylation, upon the adsorption of two polymer molecular weights was studied. The adsorption behavior was then linked to the respective surface structures via characterization of the surfaces using FTIR, NMR, and Raman techniques. In this paper role of hydrogen bonding sites and surface architecture on adsorption is discussed. Copyright 2000 Academic Press.     

Influence of substrate hydrophobicity on the adsorption of an amphiphilic diblock copolymer

The adsorption of poly(tert-butylmethacrylate)-block-poly(2-(dimethylamino-ethyl) methacrylate) (PtBUMA-b-PDMAEMA) was studied by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) analysis performed on dried samples. The copolymer was dissolved in toluene at concentrations below (0.01 wt%) and above (0.05 and 1 wt%) the CMC; silicon (SiOH) and CH(3)-grafted silicon (SiCH(3)) were used as substrates. Whatever the concentration and the substrate, a layer of individual copolymer molecules, 1.5-3 nm thick, formed rapidly. The adsorbed amount was slightly higher and the resistance to AFM tip scraping was stronger on SiOH than on SiCH(3). This is attributed to hydrogen bonding between the PDMAEMA block and the OH groups of the silicon surface, leading to polarization of the adsorbed layer. Above the CMC, on SiOH, randomly scattered dot-like features (about 5 nm high) observed by AFM were attributed to individual micelles, which were not displaced by drying. On SiCH(3), the particles found on the top of the adsorbed layer were micelle aggregates, about 50 nm thick, the lateral size of which was strongly influenced by the rate of drying. This further difference between SiCH(3) and SiOH is tentatively attributed to the exposure of PDMAEMA by the adsorbed layer formed on SiCH(3), while only PtBUMA would be exposed by the layer adsorbed on SiOH. The red blood cell shape and the size of the micelles observed in single layers indicate that the PtBUMA corona was not made compact as a result of drying.     

Evaluation of the Polymerization and Recognition Mechanism for Phenol Imprinting SPE

In order to develop more efficient preparation technologies for imprinted polymers (MIPs), the nature of pre-polymerization and molecular recognition in MIP was investigated by molecular dynamics modeling (MD), ¹H NMR, FTIR and some indirect techniques. Phenol was used as the template for the study of mechanism through the analysis of hydrogen bonding, hydrophobic and π–π bonding interaction. The 4-vinylpyridine-based MIP had the highest selectivity to its phenol template. Hydrogen bonding was proved to be present by characterizing the pre-polymerization complex and evaluating the recognition process and the effects of rebinding solvents were also studied. It was found that a good rebinding solvent should have less affinity with both template and polymer, but good solubility. MD modeling and some indirect techniques demonstrated that 4-vinylpyridine-based MIP recognized phenol mainly through hydrophobic interactions when the rebinding medium was water, while hydrogen bonding was present in the recognition process when the rebinding solvent was n-hexane.     

Adsorption/aggregation of surfactants and their mixtures at solid-liquid interfaces

Adsorption of surfactants and polymers at solid-liquid interfaces is used widely to modify interfacial properties in a variety of industrial processes such as flotation, ceramic processing, flocculation/dispersion, personal care product formulation and enhanced oil recovery. The behavior of surfactants and polymers at interfaces is determined by a number of forces, including electrostatic attraction, covalent bonding, hydrogen bonding, hydrophobic bonding, and solvation and desolvation of various species. The extent and type of the forces involved varies depending on the adsorbate and the adsorbent, and also the composition and other characteristics of the solvent and dissolved components in it. The influence of such forces on the adsorption behavior is reviewed here from a thermodynamics point of view. The experimental results from microcalorimetric and spectroscopic studies of adsorbed layers of different surfactant and polymer systems at solid-liquid interfaces are also presented. Calorimetric data from the adsorption of an anionic surfactant, sodium octylbenzenesulfonate, and a non-ionic surfactant, dodecyloxyheptaethoxyethylalcohol, and their mixtures on alumina, yielded important thermodynamic information. It was found that the adsorption of anionic surfactants alone on alumina was initially highly exothermic due to the electrostatic interaction with the substrate. Further adsorption leading to a solloid (hemimicelle) formation is proposed to be mainly an entropy-driven process. The entropy effect was found to be more pronounced for the adsorption of anionic-non-ionic surfactant mixtures than for the anionic surfactant alone. Fluorescence studies using a pyrene probe on an adsorbed surfactant and polymer layers, along with electron spin resonance (ESR) spectroscopy, reveal the role of surface aggregation and the conformation of the adsorbed molecules in controlling the dispersion and wettability of the system.     

Adhesion of polyether-modified poly(acrylic acid) to mucin

Pluronic-PAA, a thermogelling copolymer composed of side chains of poly(acrylic acid) (PAA) grafted onto a backbone of Pluronic copolymer, is of interest as a vehicle for the controlled release of compounds. An important feature of such a vehicle is its bioadhesive/mucoadhesive properties, which in the case of Pluronic-PAA are significant due to the presence of the PAA side chains. An atomic force microscopy (AFM) method has been developed and utilized to investigate the interactions between a Pluronic-PAA-modified microsphere and mucous substrates. The bioadhesive force was successfully measured, and trends were observed under conditions of varying pH and ionic strength. Pluronic-PAA exhibits significant mucoadhesion over a range of pH values, with mucoadhesion being optimal at pH 4-5 (adhesive force approximately 80 mN/cm(2)) and dropping sharply at higher pH, to a value of approximately 20 mN/cm(2) at pH 8. The mucoadhesive force decreased with increasing ionic strength, from a value of approximately 80 mN/cm(2) in 0.025 M NaCl to approximately 25 mN/cm(2) in 1.0 M NaCl. These results have been interpreted in terms of the effect of changing pH and ionic strength on electrostatic interactions and swelling of the polymer and mucin layers. Tensiometric force measurements indicated that hydrophobic interactions, as well as hydrogen bonding and electrostatic interactions, were significant in the mucoadhesion of Pluronic-PAA copolymers. Experiments with a range of Pluronic-PAA copolymers with varying PPO contents in the Pluronic segments showed that increasing the overall PPO content increased the hydrophobicity of the polymer solutions. This was reflected in the increases in the advancing contact angles with the mucin layer, indicating that hydrophobic interactions play a role in the adhesion of Pluronic-PAA to mucin.     

Sum-frequency observation of solvent structure at model chromatographic interfaces: acetonitrile-water and methanol-water systems

The adsorption of methanol-D2O and acetonitrile-D2O solutions at model chromatographic interfaces (octadecylsiloxane and quartz) was studied using sum-frequency spectroscopy. Methanol did not adsorb at either interface in detectable quantities, while acetonitrile adsorbs at the octadecylsiloxane- and quartz-solution interfaces in a concentration-dependent manner and is well ordered at the interface. Adsorption of acetonitrile was decreased by the addition of KCl at 10 and 100 mM. Acetonitrile adsorption was also observed during simulated gradient elution, demonstrating that adsorption of acetonitrile occurs on a time scale relevant to actual chromatographic separations. Examination of the OH stretch spectra of acetonitrile-H2O and methanol-H2O solutions at the interface revealed concentration-dependent changes in the acetonitrile-H2O spectra that are consistent with hydrogen bonding between interfacial water and acetonitrile, indicating that interfacial water is involved in mediating acetonitrile adsorption. The OH stretch spectra of methanol-H2O solutions showed no such changes.     

胺基化PGMA交联微球对胆红素的吸附机理

通过胺基与环氧键之间的开环反应, 用己二胺及多乙烯多胺等小分子胺化试剂对聚甲基丙烯酸缩水甘油酯(PGMA)交联微球进行了化学改性, 制得了胺基化的PGMA交联微球, 研究了该功能微球对胆红素的吸附特性, 考察了胺化试剂的分子结构、介质pH值、离子强度及温度等因素对其吸附性能的影响, 较深入地研究了吸附机理. 实验结果表明, 胺基化微球对胆红素具有强吸附作用, 吸附容量可达17.80 mg·g-1, 等温吸附服从Freundlich方程. 胺基化微球与胆红素分子之间的作用力以静电相互作用为主, 同时也存在氢键作用与疏水相互作用. 在pH 值为6 的介质中二者之间的静电作用最强, 胆红素吸附容量最高. 高离子强度不利于静电相互作用, 盐度增大使吸附容量减小. 温度升高有利于疏水相互作用而不利于氢键作用, 两种作用中占优势者主导温度对吸附容量的影响. 用己二胺改性的微球, 由于疏水相互作用的强化以及较长连接臂导致较小的空间位阻, 使其对胆红素的吸附能力明显高于多乙烯多胺改性的微球.     

Residence time, loading force, pH, and ionic strength affect adhesion forces between colloids and biopolymer-coated surfaces

Exopolymers are thought to influence bacterial adhesion to surfaces, but the time-dependent nature of molecular-scale interactions of biopolymers with a surface are poorly understood. In this study, the adhesion forces between two proteins and a polysaccharide [Bovine serum albumin (BSA), lysozyme, or dextran] and colloids (uncoated or BSA-coated carboxylated latex microspheres) were analyzed using colloid probe atomic force microscopy (AFM). Increasing the residence time of an uncoated or BSA-coated microsphere on a surface consistently increased the adhesion force measured during retraction of the colloid from the surface, demonstrating the important contribution of polymer rearrangement to increased adhesion force. Increasing the force applied on the colloid (loading force) also increased the adhesion force. For example, at a lower loading force of approximately 0.6 nN there was little adhesion (less than -0.47 nN) measured between a microsphere and the BSA surface for an exposure time up to 10 s. Increasing the loading force to 5.4 nN increased the adhesion force to -4.1 nN for an uncoated microsphere to a BSA surface and to as much as -7.5 nN for a BSA-coated microsphere to a BSA-coated glass surface for a residence time of 10 s. Adhesion forces between colloids and biopolymer surfaces decreased inversely with pH over a pH range of 4.5-10.6, suggesting that hydrogen bonding and a reduction of electrostatic repulsion were dominant mechanisms of adhesion in lower pH solutions. Larger adhesion forces were observed at low (1 mM) versus high ionic strength (100 mM), consistent with previous AFM findings. These results show the importance of polymers for colloid adhesion to surfaces by demonstrating that adhesion forces increase with applied force and detention time, and that changes in the adhesion forces reflect changes in solution chemistry.     

多糖类大分子与表面活性剂相互作用的研究进展

多糖类大分子具有天然、无毒、使用安全和可再生及来源丰富等优点. 将多糖类大分子与表面活性剂复配使用, 不仅可利用各自的优势和特性, 而且能发挥二者的协同作用, 大大改善二者的性能. 由于两者之间存在诸如静电作用、疏水作用、偶极相互作用、氢键作用、空间位阻效应等, 水体系中表面活性剂在多糖分子链上的缔合得到调控, 并引起表面活性剂的临界聚集浓度(cac)、临界胶束浓度(cmc)、结合量, 以及体系的表面吸附、界面流变性等呈现各种变化. 本文简要总结了近年来多糖类大分子与表面活性剂复配体系研究方面取得的一些进展, 述及复配体系研究中所采用的方法与手段, 主要讨论复配体系的物理化学性质以及多糖类大分子与表面活性剂相互作用的机制.     

Sorption of poly(hexamethylenebiguanide) on cellulose: mechanism of binding and molecular recognition

Antimicrobial agents such as poly(hexamethylene biguanide) (PHMB) find application in medical, apparel, and household textile sectors; although it is understood that certain concentrations need to be applied to achieve suitable performance, there has been very little work published concerning the interactions of the polymer and its adsorption mechanism on cellulose. In this paper, such physical chemistry parameters are examined and related to computational chemistry studies. Adsorption isotherms were constructed: at low concentrations, these were typical Langmuir isotherms; at higher concentrations, they were more indicative of Freundlich isotherms, attributed to a combination of electrostatic and hydrogen-bonding forces, which endorsed computational chemistry proposals. At lower concentrations, electrostatic interactions between PHMB and carboxylic acid groups in the cellulose dominate with a contribution to binding through hydrogen bonding; as the concentration of PHMB increases, hydrogen bonding with cellulose becomes increasingly dominant. At high PHMB concentrations, observations of increasing PHMB adsorption are attributed to monolayer aggregation and multilayer stacking of PHMB through electrostatic interactions with counterions and hydrogen bonding of biguanide groups.     

水介质中氢键吸附与疏水吸附协同作用的研究

研究了丙烯酸型树脂(D152)在水、乙醇和正己烷中对苯胺、N-甲基苯胺和N,N-二甲基苯胺的吸附行为.在水中D152树脂对3种吸附质的吸附亲合性随N上甲基数的增加而增大,说明疏水作用是主要的吸附机理,但其吸附焓己超出范德华力的范围而在氢键的键能范围内,故氢键吸附也同时在起作用.在正己烷中,D152树脂对3种吸附质的吸附亲合性随N上甲基数的增加而减小,与水中呈相反的趋势,说明氢键作用是主要的吸附机理.在乙醇中,D152树脂对3种吸附质均无吸附,因为疏水作用和氢键作用均受到的乙醇抑制.在水中,吸附质与树脂间的氢键作用同样受到水的抑制,但氢键吸附却依然存在,说明水介质中氢键吸附和疏水吸附可能存在一种协同作用.在热力学上对水介质中氢键吸附和疏水吸附的协同作用给于合理的解释.     

Gelation of charged bio-nanocompartments induced by associative and non-associative polysaccharides

Vesicles composed of sodium oleate (NaO) and monoolein (MO) are adequate candidates for drug nanoencapsulation and controlled release due to their stability and perceived biocompatibility. The object of the present study is to design hydrogels based on those anionic vesicles and polymers of both non-associative and associative type. The selected macromolecules were k-carrageenan (KC), carboxymethyl cellulose (CMC) and hydrophobically modified carboxymethyl cellulose (HMCMC). While the polymer-vesicle association was probed by rheology, the influence of the polymer on the vesicle stability was monitored by cryo-TEM and calorimetric measurements. The effects of the polymer on the rheological properties of surfactant aggregate solutions clearly depend on the polymer type: the storage moduli of the polymer-vesicle mixtures, compared to the vesicles alone, increases around 2 orders of magnitude if the polymer is non-associative and 4 orders of magnitude if the macromolecule is of associative type. As the vesicles are added, the non-associative polymer networks tend to be disrupted, while the networks formed by associative polymer get more robust. These observations can be explained by fundamental changes in electrostatic/hydrophobic interactions: vesicles entrapped in KC networks convert the polysaccharide in a highly charged entity and favor high electrostatic repulsions between the chains; this encourages network collapse. The opposite picture is experienced in HMCMC systems, i.e., such network is stabilized by the presence of vesicles. This is ascribed to the enhanced hydrophobic association, compensating the electrostatic repulsions between vesicles and polymer chains.