Weak Polyacid Research Articles

Born energy, acid-base equilibrium, structure and interactions of end-grafted weak polyelectrolyte layers

This work addresses the effect of the Born self-energy contribution in the modeling of the structural and thermodynamical properties of weak polyelectrolytes confined to planar and curved surfaces. The theoretical framework is based on a theory that explicitly includes the conformations, size, shape, and charge distribution of all molecular species and considers the acid-base equilibrium of the weak polyelectrolyte. Namely, the degree of charge in the polymers is not imposed but it is a local varying property that results from the minimization of the total free energy. Inclusion of the dielectric properties of the polyelectrolyte is important as the environment of a polymer layer is very different from that in the adjacent aqueous solution. The main effect of the Born energy contribution on the molecular organization of an end-grafted weak polyacid layer is uncharging the weak acid (or basic) groups and consequently decreasing the concentration of mobile ions within the layer. The magnitude of the effect increases with polymer density and, in the case of the average degree of charge, it is qualitatively equivalent to a small shift in the equilibrium constant for the acid-base equilibrium of the weak polyelectrolyte monomers. The degree of charge is established by the competition between electrostatic interactions, the polymer conformational entropy, the excluded volume interactions, the translational entropy of the counterions and the acid-base chemical equilibrium. Consideration of the Born energy introduces an additional energetic penalty to the presence of charged groups in the polyelectrolyte layer, whose effect is mitigated by down-regulating the amount of charge, i.e., by shifting the local-acid base equilibrium towards its uncharged state. Shifting of the local acid-base equilibrium and its effect on the properties of the polyelectrolyte layer, without considering the Born energy, have been theoretically predicted previously. Account of the Born energy leads to systematic, but in general small, corrections to earlier theoretical predictions describing the behavior of weak polyelectrolyte layers. However, polyelectrolyte uncharging results in a decrease in the concentration of counterions and inclusion of the Born Energy can result in a substantial decrease of the counterion concentration. The effect of considering the Born energy contribution is explored for end-grafted weak polyelectrolyte layers by calculating experimental observables which are known to depend on the presence of charges within the polyelectrolyte layer: inclusion of the Born energy contribution leads to a decrease in the capacitance of polyelectrolyte-modified electrodes, a decrease of conductivity of polyelectrolyte-modified nanopores and an increase in the repulsion exerted by a planar polyelectrolyte layer confined by an opposing wall.

Tuning Surface Mechanical Properties by Amplified Polyelectrolyte Self-Assembly: Where “Grafting-from” Meets “Grafting-to”

We report the interaction of surface-tethered weak polyacid brushes, poly(methacrylic acid), with a weak polybase poly(L-lysine)-graft-poly(ethylene glycol), in solution. The grafted polyacid brushes, grown directly from the silicon substrate by UVLED surface-initiated polymerization, act as a nanotemplate for the solution-phase polybase, which penetrates into the brushes, forming a polyelectrolyte complex (PEC), whose mechanical and nanotribological properties are markedly influenced by the electrostatic assembly conditions. The mechanical effects are amplified due to the architecture of the specific polybase used, which contributes approximately 2k Da per unit charge to the overall system, resulting in an efficient filling of the polyacid brushes, which thus acts as a scaffold. The distribution of the adsorbed copolymers in the PEC films has been investigated by means of confocal microscopy. The unique structure of the PEC films provides a system whose mechanical and nanotribological properties can be tuned over a wide range.

Effect of Sequence on the Ionization Behavior of a Series of Amphiphilic Polypeptides

The behavior of five polypeptides made of hydrophilic and pH-responsive aspartic acid (Asp) and hydrophobic phenylalanine (Phe), which had been prepared by stitching together short well-defined sequences of Asp and Phe, was studied as a function of pH. The effect of pH on these polypeptides referred to as (Asp3Phe1)n, (Asp2Phe1)n, (Asp1Phe1)n, (Asp1Phe2)n, and (Asp1Phe3)n varied dramatically depending on their constituting sequence. The more hydrophobic polypeptides (Asp1Phe2)n and (Asp1Phe3)n behaved as if the Asp's were isolated from each other and showed an apparent pKa (pKa(app)) that remained constant with level of ionization (α = [Asp(-)]/[Asp]total) and equaled 5.4 and 6.4, respectively. The more hydrophilic polypeptides (Asp3Phe1)n and (Asp2Phe1)n behaved like weak polyacids showing a linear increase in pKa(app) with increasing α. The pKa(app) of (Asp1Phe1)n showed a trend as a function of α intermediate between the Asp-rich and Phe-rich polypeptides, behaving as if the Asp's were isolated at low α values (<0.35) but acting as a weak polyacid for large α values (>0.35). The effect that α, and thus the charge density of the polypeptides, had on the collapse and aggregation of the polypeptides was characterized by conducting static light scattering and fluorescence measurements. Static light scattering measurements demonstrated that all polypeptides precipitated and aggregated in solution at a critical charge density of 0.2. Fluorescence measurements with pyrene indicated that this behavior was due to the formation of Phe aggregates in water. Together, these experiments provide a complete description of how pH affects the behavior of a series of unique amphiphilic polypeptides designed with a well-defined sequence.

Charged microcapsules for controlled release of hydrophobic actives. Part I: encapsulation methodology and interfacial properties

Highly charged microcapsules have been prepared using the internal phase separation technique. The charges are introduced by using ionic dispersants, which have been characterized with respect to surface activity with a quartz crystal microbalance with dissipation monitoring and with optical tensiometry. The long-term stability of the microcapsule suspension without excess dispersant, as well as the stability at high ionic strength, have been investigated. Three types of ionic dispersants have been evaluated: a weak polyacid (poly(methacrylic acid)), a small set of ionic amphiphilic block copolymers of poly(methyl methacrylate)-block-poly(sodium (meth)acrylate) type and an oil-soluble anionic surfactant, sodium 1,5-dioxo-1,5-bis(3,5,5-trimethylhexyloxy)-3-((3,5,5-trimethylhexyloxy)carbonyl)pentane-2-sulfonate, in combination with a water-soluble polycation, poly(diallyldimethylammonium chloride). The block copolymer based microcapsule suspension is characterized by a long-term stability, even at high ionic strength, provided by electrostatic and steric stabilization. The weak polyacid based microcapsule suspension is stable for a few weeks, after which aggregation starts due to desorption of the dispersant. The surfactant–polycation based microcapsules appear to have a multicore morphology in contrast to the weak polyacid or block copolymer based microcapsules, which are core–shell particles.

Tunable pH and temperature response of weak polyelectrolyte brushes: role of hydrogen bonding and monomer hydrophobicity

We report on weak polyacid brushes with highly tunable pH and temperature response characteristics. This was achieved by synthesizing a series of homo- and copolymers which contain 2-alkylacrylic acids (aAAs) of increased hydrophobicity, i.e. acrylic acid (AA), methacrylic acid (MAA), or 2-ethylacrylic acid (EAA), using surface-initiated reversible addition–fragmentation chain transfer (SI-RAFT) polymerization. As revealed by contact angle measurements, in situ ellipsometry and AFM studies of brush swelling, the pH-response of PAA and PMAA brushes was similar, with brushes remaining highly swollen (swelling ratio 2.5–3.0) at low pH values. The PEAA brush, however, was unique as it showed low degrees of water uptake ( 70°) contact angles in the entire pH region from 2 to 8. Copolymer brushes of aAAs with N-isopropylacrylamide (NIPAM), denoted as P(AA-co-NIPAM), P(MAA-co-NIPAM) and P(EAA-co-NIPAM), demonstrated dual pH and temperature response, which was strongly dependent on the type of aAA co-monomer. P(AA-co-NIPAM) and P(MAA-co-NIPAM) brushes underwent large-amplitude pH-induced changes in brush swelling and water contact angle in the range of pH from 3 to 6, and were only weakly responsive to temperature in the transition region. In contrast, more hydrophobic P(EAA-co-NIPAM) brushes demonstrated both pH and temperature responses at physiologically relevant neutral/basic pH values even when the content of EAA units in the copolymer was as high as ∼50%. We discuss the role of inter- and intra-molecular hydrogen bonding and monomer hydrophobicity and ionization (quantified by FTIR) in determining pH ranges for brush response. These findings might enable control of molecular/cellular adhesion and flow at interfaces potentially useful in microfluidic and biomedical applications.

Multilayered polyelectrolyte complex based solvent resistant nanofiltration membranes prepared from weak polyacids

Alternating deposition of oppositely charged polyelectrolyte (PE) complexes (PECs) were recently reported to create stable solvent resistant nanofiltration (SRNF) membranes with high flux and selectivity. The new combination of poly(diallyldimethylammonium chloride) (PDDA) with a weak polyacid (polyacrylic acid, PAA) was investigated in this report, since the charge density of these PEC based membranes can be affected by more factors than with strong polyacids, such as salt concentration and pH. Thus offers more possibilities to control membrane morphology and performance. Prepared membranes showed more than 90% retention for Rose Bengal (RB) from different solvents, proving the good potential of these membranes in SRNF applications.

Nanoparticle Modification by Weak Polyelectrolytes for pH-Sensitive Pickering Emulsions

The affinity of weak polyelectrolyte coated oxide particles to the oil-water interface can be controlled by the degree of dissociation and the thickness of the weak polyelectrolyte layer. Thereby the oil in water (o/w) emulsification ability of the particles can be enabled. We selected the weak polyacid poly(methacrylic acid sodium salt) and the weak polybase poly(allylamine hydrochloride) for the surface modification of oppositely charged alumina and silica colloids, respectively. The isoelectric point and the pH range of colloidal stability of both particle-polyelectrolyte composites depend on the thickness of the weak polyelectrolyte layer. The pH-dependent wettability of a weak polyelectrolyte-coated oxide surface is characterized by contact angle measurements. The o/w emulsification properties of both particles for the nonpolar oil dodecane and the more polar oil diethylphthalate are investigated by measurements of the droplet size distributions. Highly stable emulsions can be obtained when the degree of dissociation of the weak polyelectrolyte is below 80%. Here the average droplet size depends on the degree of dissociation, and a minimum can be found when 15 to 45% of the monomer units are dissociated. The thickness of the adsorbed polyelectrolyte layer strongly influences the droplet size of dodecane/water emulsion droplets but has a less pronounced impact on the diethylphthalate/water droplets. We explain the dependency of the droplet size on the emulsion pH value and the polyelectrolyte coating thickness with arguments based on the particle-wetting properties, the particle aggregation state, and the oil phase polarity. Cryo-SEM visualization shows that the regularity of the densely packed particles on the oil-water interface correlates with the degree of dissociation of the corresponding polyelectrolyte.

Molecular modeling of responsive polymer films

Fil: Tagliazucchi, Mario Eugenio. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Oficina de Coordinacion Administrativa Ciudad Universitaria. Instituto de Quimica, Fisica de los Materiales, Medioambiente y Energia. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Quimica, Fisica de los Materiales, Medioambiente y Energia; Argentina. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Departamento de Quimica Inorganica, Analitica y Quimica Fisica; Argentina

Synthesis, characterization and swelling behaviour of poly(methacrylic acid) brushes synthesized using atom transfer radical polymerization

Poly(methacrylic acid) brushes have been prepared utilizing the “grafting from” technique and a living radical synthesis route using a two stage process. Firstly a poly(1-ethoxyethyl methacrylate) brush was synthesized by atom transfer radical polymerization and then thermally decomposed to poly(methacrylic acid). The swelling behaviour of the weak polyacid brush was investigated as a function of pH and salt concentration in aqueous solutions using atomic force microscopy. Force pulling measurements were used to establish the molecular weight and the grafted chain density. The swelling transition was found to be at pH 9; which is significantly different to the pKa (5.5) of untethered poly(methacrylic acid). We attribute this large shift in pKa to the high grafting density of these brushes. This can be explained as a result of the Coulombic repulsion of neighbouring charges. High salt concentrations (0.3M Na+) also collapse the brush layer. Conversely low salt concentrations cause an increase in the thickness of the brush, a behaviour expected for osmotic brushes.

PH-Dependent Behaviors of Electroactive Myoglobin Loaded into Layer-by-Layer Films Assembled with Alginate and Hydroxyethyl Cellulose Ethoxylate

In the present work, strong polybase quaternized hydroxyethyl cellulose ethoxylate (HECE) and weak polyacid alginate (AA) were assembled into {HECE/AA} n layer-by-layer (LBL) films on electrodes by electrostatic interaction between them, and the films were then immersed in myoglobin (Mb) solution to load Mb into the films, designated as {HECE/AA}n-Mb. The {HECE/AA}n-Mb films showed a nearly reversible cyclic voltammetric (CV) peak pair at about -0.34 V vs SCE in pH 7.0 buffers for Mb heme Fe(III)/Fe(II) redox couple, and the surface concentration of electroactive Mb in the films (Gamma*) was affected significantly by the pH of Mb loading solution and testing solution. The amount of Mb loaded from pH 5.0 solution was much larger than that from pH 9.0 solution, which is mainly attributed to the higher degree of swelling, porosity, and permeability of {HECE/AA}n films at pH 5.0 than at pH 9.0. In addition, the electrostatic interaction between Mb and the AA component in the films might also play an important role in Mb loading. The pH of the testing solution where {HECE/AA}n-Mb films were tested by CV also influenced the Gamma* value, showing that the fraction of electroactive Mb among the total Mb loaded into the films increased remarkably as the pH of the testing solution decreased. This result is rationalized in terms of the pH-dependent film permeability toward counterions and the electron-hopping mechanism in electron transfer of redox proteins in the film phase. This model system may provide a general and effective approach to control the electroactivity of immobilized redox proteins in the multilayer assembly containing weak polyions by adjusting pH and may guide us to develop the new kind of controllable electrochemical biosensors based on the direct electrochemistry of enzymes.

Multilayer Polymeric Nanoparticles Based on Specific Interactions in Solution: Polystyrene-block-poly(methacrylic acid) Micelles with Linear Poly(2-vinylpyridine) in Aqueous Buffers

Polymeric micelles of polystyrene-block-poly(methacrylic acid) with the shell containing various amounts of poly(2-vinylpyridine) chains were prepared by dialysis from 1,4-dioxane-rich mixtures into alkaline aqueous solutions. The structure of the polymeric nanoparticles was studied by light scattering, atomic force microscopy, fluorometry, and capillary zone electrophoresis. The presence of both weak polyacid and weak polybase in the corona allows the micelles to form fairly stable solutions in a broad pH range. Poly(methacrylic acid) blocks are dissociated in basic buffers, while poly(2-vinylpyridine) chains stabilize the micelles in acidic solutions. Besides the water-swollen shell, the inner parts of the micelles consist of the kinetically frozen polystyrene core and relatively rigid layer of poly(methacrylic acid) and poly(2-vinylpyridine) segments. An insufficient number of stabilizing polymer chain segments results in the aggregation of the micelles into clusters.

Novel Electrospun Nanofibers Composed of Polyelectrolyte Complexes

AbstractA simple method to obtain novel nanofibers composed of polyelectrolyte complexes (PECs) has been proposed. It consists of the electrospinning of a mixed homogeneous solution of polyelectrolyte partners, and the formation of PEC during the electrospinning. This was achieved by careful choice of the composition of the spinning solutions. Chitosan was the polycationic partner, with either a weak polyacid [poly(acrylic acid), PAA] as a counterpart or a strong one [poly(2‐acrylamido‐2‐methylpropanesulfonic acid), PAMPS]. The fibrous mats were composed of nanofibers with mean diameters of ca. 100 nm. They retained their integrity over the pH range which is typical of the corresponding PEC.magnified image

Polyelectrolyte multilayers of poly(vinylamine hydrochloride‐co‐N‐vinylformamide) with variable primary amine content and a weak polyacid poly(acrylic acid)

AbstractPoly(vinylamine hydrochloride‐co‐N‐vinylformamide) [poly(VAm‐co‐NVF)] with variable VAm content, and a weak polyacid poly(acrylic acid) were assembled on a quartz crystal microbalance (QCM) substrate from their aqueous solutions, thus forming polyelectrolyte multilayers. The effects of varying the VAm content on assembly profiles and film structures were analyzed by quantitative QCM analysis, attenuated total reflection spectra techniques, and atomic force microscopic observation. At a VAm content of less than 40% of the total number of poly(VAm‐co‐NVF) units, the layer‐by‐layer assembly did not proceed, and the frequency shift of the QCM zigzagged with the step number. Above 40% VAm content, the frequency increased continuously with an increasing number of steps. The assembly amount was also maximal at 40% VAm content. The films obtained swelled with water molecules, and this swelling was followed by an increase in thickness in the aqueous phase. The results obtained were compared to those obtained from a combination of poly(VAm‐co‐NVF) and a strong polyacid, poly(sodium styrenesulfonate). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3927–3933, 2006

Reciprocating Power Generation in a Chemically Driven Synthetic Muscle

A scalable synthetic muscle has been constructed that transducts nanoscale molecular shape changes into macroscopic motion. The working material, which deforms affinely in response to a pH stimulus, is a self-assembled block copolymer comprising nanoscopic hydrophobic domains in a weak polyacid matrix. A device has been assembled where the muscle does work on a cantilever and the force generated has been measured. When coupled to a chemical oscillator this provides a free running chemical motor that generates a peak power of 20 mW kg(-1) by the serial addition of 10 nm shape changes that scales over 5 orders of magnitude. It is the nanostructured nature of the gel that gives rise to the affine deformation and results in a robust working material for the construction of scalable muscle devices.

Multilayers of a Globular Protein and a Weak Polyacid: Role of Polyacid Ionization in Growth and Decomposition in Salt Solutions

Thin films obtained from a layer-by-layer deposition of a weak polycarboxylic acid and a positively charged globular protein were studied by in situ ATR-FTIR. The system was chicken egg lysozyme (Lys), bovine pancrease ribonuclease A (RNase), or bovine gamma-globulin (IgG) self-assembled with polycarboxylic acids. When the pH value was lowered below a critical point, the growth of films and their tolerance to decomposition by added sodium chloride improved dramatically. Stabilization of protein/polyacid films in salt solutions at lower pH values occurred due to the onset of nonelectrostatic interactions to intermolecular binding within protein/polyacid multilayers and was controlled by polyacid ionization within the film rather than the pH of the external solution. A fractional ionization of polyacid in the pH-stabilization region was lower with protein-containing films than for polyacid/linear polycation films, reflecting hindrance of the inter-association of protonated carboxylic groups by protein globules. Practical ramifications of the pH-stabilization effect might extend to areas of biotechnology and biomaterials.

Effect of Salt Concentration on the Nanostructure of Weak Polyacid Brush in the Amphiphilic Polymer Monolayer at the Air/Water Interface

The effect of salt concentration on the nanostructure of a spread monolayer of ionic amphiphilic diblock copolymer, (diethylsilacyclobutane)m-b-(methacrylic acid)n, at the air-water interface was directly investigated by in situ X-ray reflectivity and neutron reflectivity techniques. Previously, we had found that a poly(methacrylic acid) (PMAA) hydrophilic layer under the water was not in the form of a simple polyelectrolyte brush but consisted of a dense carpet upper layer and a diffuse brush lower layer when the hydrophilic chain was long enough. Here we observed this double layer formation in the monolayer in aqueous NaCl solution at a constant surface pressure. The effect of salt added to the subphase differed with the salt concentrations, that is, below or above 0.1 M. In the presence of NaCl up to 0.1 M, both the hydrophobic layer and brush layer thicknesses decreased. On the other hand, both of them increased in the presence of NaCl above 0.1 M. Also, the carpet layer thickness was almost constant independent of the salt concentration. In addition, the brush top roughness showed a maximum in the presence of 0.1 M NaCl. The increase of the charge number on the PMAA chain and the screening effect of the Coulomb interaction by added salt ions were considered to be responsible for these phenomena.

Exceptional gas permeation selectivity of a glued Langmuir-Blodgett bilayer by pH control.

The monolayer properties of 5,11,17,23,29,35-hexakis[(N,N,N-trimethylamonium)-N-methyl-37,38,39,40,41,42-hexakis-n-hexadecyloxy-calix[6]arene hexachloride (1) have been characterized over aqueous solutions of poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA) as a function of pH. At high pH values (e.g., pH 10), such monolayers show relatively low surface viscosities. At low pH (e.g., pH 4.4), these monolayers exhibit relatively high surface viscosities. The barrier properties of single Langmuir-Blodgett bilayers of 1, which have been ionically cross-linked (i.e., "glued together") with PAA were found to correlate with changes in surface viscosity. Thus, bilayers that were fabricated under low pH conditions exhibited high permeation barriers and high permeation selectivity with respect to He and N(2). Given the extreme thinness of these glued bilayers (ca. 6 nm), the optimized He/N(2) selectivity of ca. 1000 is extraordinary. These results, taken together, demonstrate the feasibility of fine tuning the surface viscosity of monolayers of 1, and also the barrier properties of corresponding glued bilayers, by adjusting the pH of an aqueous subphase that contains a weak polyacid.

Charge Regulation of Interacting Weak Polyelectrolytes

We introduce a generalized nonuniform mean-field formalism to describe the dissociation of weak rodlike polyelectrolytes (PEs). Our approach allows for two-sublattice symmetry breaking which in titration curves is associated with a plateau for intermediate dissociation degrees. We first test our method in the case of a single weak PE by comparison with exact enumeration studies and show that it gives quantitatively accurate results for the dissociation degree in the full range of pH values and specifically performs much better than the nearest-neighbor approximation (where exact solutions are possible). We then study charge regulation of the coupled system of a weak polyacid and a weak polybase as a function of their mutual distance, which has some relevance for PE multilayer formation and for PE complexation. An intricate interplay of the degree of dissociation and the effective interaction between the PEs as a function of their mutual distance is found.

Polyelectrolyte Multilayers of Weak Polyacid and Cationic Copolymer: Competition of Hydrogen-Bonding and Electrostatic Interactions

We report on the competitive role of hydrogen bonding and electrostatic interactions in growth and stability of polyelectrolyte multilayers (PEMs) in a wide range of pH. The system was a cationic copolymer of acrylamide and dimethyldiallylammonium chloride (PAAm-DMDAAC) containing 50% cationic units and poly(methacrylic acid) (PMAA) as a polyacid. The amounts of polymers adsorbed and ionization of carboxylic groups within a film were quantified using in situ FTIR-ATR (Fourier transform infrared spectroscopy in attenuated total reflection). The results were contrasted with the stability of films formed from polyacrylamide (PAAm) and PMAA. In the PAAm/PMAA system, interlayer adhesion occurred through hydrogen-bonding interactions, and the multilayer decomposed at pH > 5.5. However, the PAAm-DMDAAC/PMAA multilayers produced at low pH could be stabilized at a pH as high as 8 with transition to electrostatic interactions. With films deposited at pH = 2 from low ionic strength solutions, asymmetric release of P...

Polyelectrolytic Behavior of a Novel Fluorine-Containing Ionomer, PPFNA

Solution properties of a novel fluorine-containing ionomer PPFNA were studied by pH titration, conductivity, and viscosity measurements. This polymer is a poly(carboxylic acid) but dissociates strongly, resulting in a low pH value and a high specific conductance at low degrees of neutralization. When the solution was neutralized with NaOH, the conductance decreased sharply at first and then decreased gradually until full neutralization. This conductometric titration profile indicates that this polymer is a fairly strong polyelectrolyte but not a typical strong one such as poly(styrene sulfonic acid) or aliphatic ionenes. The pH measurement showed that this polymer is a strong polyacid, although the titration profile changed slightly upon the addition of salt. The reduced viscosity of the salt-free solution was well fitted to Fuoss' equation, specific to polyelectrolyte solutions. Upon the addition of salt, however, the viscosity−neutralization profile became rather similar to that of weak polyacid, and th...