Direct surface force measurements of polyelectrolyte multilayer films containing nanocrystalline cellulose

Polyelectrolyte multilayer films containing nanocrystalline cellulose (NCC) and poly(allylamine hydrochloride) (PAH) make up a new class of nanostructured composite with applications ranging from coatings to biomedical devices. Moreover, these materials are amenable to surface force studies using colloid-probe atomic force microscopy (CP-AFM). For electrostatically assembled films with either NCC or PAH as the outermost layer, surface morphology was investigated by AFM and wettability was examined by contact angle measurements. By varying the surrounding ionic strength and pH, the relative contributions from electrostatic, van der Waals, steric, and polymer bridging interactions were evaluated. The ionic cross-linking in these films rendered them stable under all solution conditions studied although swelling at low pH and high ionic strength was inferred. The underlying polymer layer in the multilayered film was found to dictate the dominant surface forces when polymer migration and chain extension were facilitated. The precontact normal forces between a silica probe and an NCC-capped multilayer film were monotonically repulsive at pH values where the material surfaces were similarly and fully charged. In contrast, at pH 3.5, the anionic surfaces were weakly charged but the underlying layer of cationic PAH was fully charged and attractive forces dominated due to polymer bridging from extended PAH chains. The interaction with an anionic carboxylic acid probe showed similar behavior to the silica probe; however, for a cationic amine probe with an anionic NCC-capped film, electrostatic double-layer attraction at low pH, and electrostatic double-layer repulsion at high pH, were observed. Finally, the effect of the capping layer was studied with an anionic probe, which indicated that NCC-capped films exhibited purely repulsive forces which were larger in magnitude than the combination of electrostatic double-layer attraction and steric repulsion, measured for PAH-capped films. Wherever possible, DLVO theory was used to fit the measured surface forces and apparent surface potentials and surface charge densities were calculated.     

Heptakis(2-O-methyl-3,6-di-O-sulfo)-beta-cyclodextrin: a single isomer, 14-sulfated beta-cyclodextrin for use as a chiral resolving agent in capillary electrophoresis

The first single-isomer, 14-sulfated beta-cyclodextrin, the sodium salt of heptakis(2-O-methyl-3,6-di-O-sulfo)-beta-cyclodextrin (HMdiSu) has been used to separate 24 pharmaceutical weak base enantiomers in pH 2.5 background electrolytes using capillary electrophoresis. For the weakly binding bases, the cationic effective mobilities decreased, approached zero, and then increased again. For the strongly binding bases, the cationic effective mobilities decreased, became anionic at very low concentrations of HMdiSu, passed an anionic mobility maximum, then decreased again as the HMdiSu concentration was increased. Viscosity corrections according to Walden's rule did not eliminate these unexpected effective mobility extrema. The mobility extrema were rationalized by extending the charged resolving agent migration model (CHARM model) to include ionic strength effects.     

Complexation between low-molecular-weight cationic ligands and negatively charged polymers as studied by capillary electrophoresis frontal analysis

The potential of using capillary electrophoresis frontal analysis for the study of low-molecular-weight ligand-polyelectrolyte interactions was assessed. The interaction of the ligands 1-propylpyridinium bromide, 2-propylisochinolinium bromide, and paraquat with the polymer dextran sulfate was investigated as a function of polymer concentration and ionic strength of the buffer solution. Linear binding isotherms were obtained and association constants were determined. The complex formation was independent of the dextran sulfate concentration at low ionic strength. Ligand-polyelectrolyte interactions were strongly dependent on the ionic strength. The interaction of the divalent cation paraquat with the dextran sulfate was much stronger than the interactions of the monovalent cationic ligands with the polyelectrolyte. The binding data obtained were in accord with results obtained by equilibrium dialysis. Capillary electrophoresis frontal analysis has the potential to become a valuable tool for characterization of ligand-polyelectrolyte interactions in drug design as well as in other areas.     

Nanocomposites based on cationic polyelectrolytes and silver nanoparticles: Synthesis,characterization, molybdate retention and antimicrobial activity

The objective of this work was to synthesize nanocomposites based on cationic polyelectrolytes and silver nanoparticles using poly(N-vinylbenzyl-N-triethylammonium chloride) as polymer phase. For that, a nanostructured crosslinker was synthesized from silver nanoparticles (AgNPs) and acrylic acid. Molybdate retention properties of nanocomposites were studied in function of pH and ionic strength. In addition, their antimicrobial properties were evaluated against E. coli and S. aureus. It was evidenced that AgNPs can be stabilized using acrylic acid and that this material can be incorporated to the polymer phase during polymerization by free radical of cationic monomers. The effect of pH on retention of molybdate, by the nanostructured polymer, was significant only to low ionic strength (the order seen was pH 5.0 > pH 7.0 > pH 9.0 for 0.0% NaCl). Results suggest that the main interaction influencing the molybdate retention is electrostatic in nature. Finally, antimicrobial activity was enhanced by incorporation of polymerizable nanostructured crosslinker based on AgNPs.     

Preparation and evaluation of an imidazole-coated capillary column for the electrophoretic separation of aromatic acids

An imidazole-coated capillary column for electrophoresis has been prepared by means of organosilanization. With mesityl oxide as neutral marker, the results indicated that the electroosmotic flow of the bonded phase displays a dramatic difference in pH dependence in comparison with that of the bare fused-silica column. The presence of positive charges on the coating surface and the anionic exchange property, due to the cationic property of the imidazole group at pH values below 6, allows the separation of geometric isomers that are very similar in ionic mobility. Separation parameters including buffer composition and concentration, pH, applied voltage, and the influence of other additives were investigated. By using acetate buffer (100 mM, pH 5.2) and an applied voltage of -15 kV with UV detection at 212 nm, the separation of 11 aromatic acids including mono-, di-, tri- and tetra-carboxylic acids could be achieved in less than 14 min. The average plate number was 3 x 10(5)/m. With acetate buffer (25 mM, pH 5.5) and an applied voltage of -25 kV, the addition of silver nitrate or beta-cyclodextrin significantly improved the resolution of some more highly charged carboxylic acids.     

Effect of polyelectrolytes and polyelectrolyte mixtures on the electrokinetic potential of dispersed particles. 2. Electrokinetic potential of silica particles in electrolyte, polyelectrolyte and polyelectrolyte mixtures solutions

The effect pH, ionic strength (KCl concentration), weakly and medium charged anionic and cationic polyelectrolytes (PEs) as well as their binary mixtures on the electrokinetic potential of silica particles as a function of the polyelectrolyte/mixture dose, its composition, charge density (CD) of the PE, and way of adding the polymers to the suspension has been studied. It has been shown that addition of increasing amount of anionic PEs increases the absolute value of the negative zeta-potential of particles at pH > pH isoelectric point (IEP = 2.5); this increase is stronger the charge density of the polyelectrolyte is higher. Adsorption of cationic polyelectrolytes at these pH values gives a significant decrease in the negative ζ-potential and overcharging the particles; changes in the ζ-potential are more pronounced for PE samples with higher CD. In mixtures of cationic and anionic PE at pH > pHIEP, the ζ-potential of particles is determined by the adsorbed amount of the anionic polymer independently of the CD of PEs, the mixture composition and the sequence of addition of the mixture components. Unexpectedly, the ζ-potential of silica at pH = 2.1, i.e. < pHIEP, turned out to be positive in the presence of both anionic PE and cationic + anionic PE mixtures. This is explained by formation (and adsorption onto positively charged silica surface) of pseudo-cationic PEs from anionic ones due to transfer of protons from the solution to the amino-group of the anionic polymer. Considerations about the role of coulombic and non-coulombic forces in the mechanism of PE adsorption are presented.     

ITP in dynamically double-coated fused-silica capillaries

Bidirectional ITP in fused-silica capillaries double-coated with Polybrene and poly-(vinylsulfonate) is a robust approach for analysis of low-molecular-mass compounds. EOF towards the cathode is strong (mobility >4.0 x 10(-8) m(2)/Vs) within the entire pH range investigated (2.40-8.08), dependent on ionic strength and buffer used and, at constant ionic strength, higher at alkaline pH. Electrokinetic separations and transport in such coated capillaries can be described with a dynamic computer model which permits the combined simulation of electrophoresis and electroosmosis in which the EOF is predicted either with a constant (i.e. pH- and ionic strength-independent) or a pH- and ionic strength-dependent electroosmotic mobility. Detector profiles predicted by computer simulation agree qualitatively well with bidirectional isotachopherograms that are monitored with a setup comprising two axial contactless conductivity detectors and a UV absorbance detector. The varying EOF predicted with a pH- and ionic strength-dependent electroosmotic mobility can be regarded as being realistic.     

Electrophoretic mobility measurements of fluorescent dyes using on-chip capillary electrophoresis

We present an experimental study of the effect of pH, ionic strength, and concentrations of the electroosmotic flow (EOF)-suppressing polymer polyvinylpyrrolidone (PVP) on the electrophoretic mobilities of commonly used fluorescent dyes (fluorescein, Rhodamine 6G, and Alexa Fluor 488). We performed on-chip capillary zone electrophoresis experiments to directly quantify the effective electrophoretic mobility. We use Rhodamine B as a fluorescent neutral marker (to quantify EOF) and CCD detection. We also report relevant acid dissociation constants and analyte diffusivities based on our absolute estimate (as per Nernst-Einstein diffusion). We perform well-controlled experiments in a pH range of 3-11 and ionic strengths ranging from 30 to 90 mM. We account for the influence of ionic strength on the electrophoretic transport of sample analytes through the Onsager and Fuoss theory extended for finite radii ions to obtain the absolute mobility of the fluorophores. Lastly, we briefly explore the effect of PVP on adsorption-desorption dynamics of all three analytes, with particular attention to cationic R6G.     

Factors Responsible for the Electrophoretic Behavior of Carboxylic Acid and Triazine Derivatives under Conditions of Capillary Zone Electrophoresis and Micellar Electrokinetic Chromatography

The effects of the pH, nature, and ionic strength of the running buffer; temperature; and surfactants, organic solvents, and macrocyclic compounds added to the buffer solution on the electrophoretic separation parameters of anionic, cationic, and neutral components of complex mixtures of organic compounds under the conditions of capillary zone electrophoresis and micellar electrokinetic chromatography. Pesticides from the series of chlorophenoxycarboxylic acids and triazines, as well as amino acids and substituted benzoic acid derivatives, were used as model systems. The predominant role of the addition of macrocyclic reagents, in particular, -cyclodextrin, as buffer electrolyte components was noted.     

The Interaction between High-Molecular-Weight Flocculents and Ionic Surfactants

The interaction between the anionic and cationic polyelectrolytes of various molecular masses and charges and the ionic surfactants in aqueous and salt solutions is studied by viscometry, conductometry, light scattering, and electrophoresis. Oppositely charged molecules of surfactant and polymer form strong complexes due to the forces of electrostatic attraction that is manifested in a significant decrease in the viscosity and light transmission, as well as in the relative reduction in solution conductivity. As the surfactant/polyelectrolyte ratio increases, the forming complexes precipitated and then dissolved again. In the case of strongly charged polyelectrolytes, the partial dissolution of precipitates was observed preceding the wide region of destabilization. In this region, the value of surfactant/polyelectrolyte charge ratio reaches 3–4. The interaction between the cationic surfactants and anionic polyelectrolyte increases with the lengthening of alkyl radical, thus indicating the presence of cooperative interactions between the surfactant molecules bonded to polymer and the important role of relevant hydrophobic interactions. As a result, the interaction between the high-molecular-weight anionic polyelectrolytes and anionic surfactants containing aromatic core takes place in some cases.     

Prediction of the swelling behaviour of amphiphilic hydrogels and the determination of average molecular weight between cross-links

Prediction of swelling behaviour of hydrogels containing cationic and anionic moieties, sensitive to pH and ionic strength changes of the swelling medium was investigated. The equations derived for the prediction of the theoretical swelling curves are based on the phantom network theory and the approaches of Peppas et al. For all predictions, a number of polymer based parameters, solution property parameters and polymer–solvent combination type parameters were evaluated typical of amphiphilic copolymers. The advantages of the derived equations for the determinations of average molecular weight between the cross-links, and also polymer–solvent interaction parameter have been exemplified.     

Modification of the electrokinetic properties of reversible electrophoresis gels for the separation and preparation of DNA

The effect of adding linear polymers to a novel reversible electrophoretic was measured. Reversible gels are formed using the polyanionic carbohydrate polymer, gellan gum. Gellan gum forms strong stable gels in the presence of divalent cations or diamines. The gels are reversible (return to solution) by changing the ionic environment or pH. Gellan gum is an anionic polymer, and the electrophoresis gels have considerable electroosmotic flow (EOF) toward the negative electrode. We measured the EOF in gellan gum electrophoresis gels as a function of gel concentration, buffer composition, and linear polymer additive. The linear polymers used in this study were polyethylene oxide and hydroxyethyl cellulose. Both polymers reduced EOF in the gels, in a manner dependent on molecular weight. Polymers with high molecular weight were more effective at reducing EOF. The addition of polymers increased the resolution of low molecular weight DNA. Native gellan gum resolved DNA from approx 50,000 to 1000 bp. Addition of the polymers resolved DNA down to approx 50 bp, in some instances. The influence of the polymers on circular plasmid DNA was also investigated. Addition of high molecular weight polyethylene oxide reduced the electrophoretic mobility of the nicked circular form compared to the supercoiled form.     

Influence of buffer composition on the capillary electrophoretic separation of carbon nanoparticles

Carbon nanoparticles obtained from the flame of an oil lamp were examined by means of capillary electrophoresis. The influence of buffer composition on the separation of the mixture of negatively charged carbon nanoparticles was studied by varying buffer selection, pH, and concentration. The electrophoretic pattern was affected by both the co- and counter-ion in the buffer solution, influencing selectivity and peak shape. The capillary electrophoretic separations at different pH revealed species with large electrophoretic mobilities under a wide range of pH. The mobility of selected species in the mixture of nanoparticles showed a strong dependence upon the solution ionic strength. The mobility of these nanoparticles as a function of ionic strength was compared to classical electrokinetic theory, suggesting that under the experimental conditions utilized, the species are small, highly charged particles with appreciable zeta potentials, even at low pH.     

Capillary electrophoretic studies on the migration behavior of cationic solutes and the influence of interactions of cationic solutes with sodium dodecyl sulfate on the formation of micelles and critical micelle concentration

The migration behavior of cationic solutes and influences of the interactions of cationic solutes with sodium dodecyl sulfate (SDS) on the formation of micelles and its critical micelle concentration (CMC) were investigated by capillary electrophoresis at neutral pH. Catecholamines and structurally related compounds, including epinephrine, norepinephrine, dopamine, norephedrine, and tyramine, which involve different extents of hydrophobic, ionic and hydrogen-bonding interactions with SDS surfactant, are selected as cationic solutes. The dependence of the effective electrophoretic mobility of cationic solutes on the concentration of surfactant monomers in the premicellar region provides direct evidence of the formation of ion-pairs between cationic solutes and anionic dodecyl sulfate monomers. Three different approaches, based on the variations of either the effective electrophoretic mobility or the retention factor as a function of surfactant concentration in the premicellar and micellar regions, and the linear relationship between the retention factor and the product of a distribution coefficient and the phase ratio, were considered to determine the CMC value of SDS micelles. The suitability of the methods used for the determination of the CMC of SDS with these cationic solutes was discussed. Depending on the structures of cationic solutes and electrophoretic conditions, the CMC value of SDS determined varies in a wide concentration range. The results indicate that, in addition to hydrophobic interaction, both ionic and hydrogen-bonding interactions have pronounced effects on the formation of SDS micelles. Ionic interaction between cationic solutes and SDS surfactant stabilizes the SDS micelles, whereas hydrogen-bonding interactions weakens the solubilization of the attractive ionic interaction. The elevation of the CMC of SDS depends heavily on hydrogen-bonding interactions between cationic solutes and SDS surfactant. Thus, the CMC value of SDS is remarkably elevated with catecholamines, such as epinephrine and norepinephrine, as compared with norephedrine. In addition, the effect of methanol content in the sample solution of these cationic solutes on the CMC of SDS was also examined.     

Separation of microorganisms using electromigration techniques

Like other colloidal particles bacteria have a surface charge that originates from the ionization of surface molecules and of the adsorption of ions from solution. Bacterial cell wall and membranes containing numerous proteins, lipid molecules, teichoic acids, lipopolisaccharides which give them characteristic charge. Therefore, bacterial cells undergo electrophoresis in a free solution with their own mobility depending on ionic strength and pH of buffer solution. Various electromigration techniques can be used to separate and determine the intact cells. Successful separation of five species of bacteria was obtained using a trimethylchlorosilane-modified capillary and a divinylbenzene-modified with suppressed EOF over a short distance (8.5 cm). The utilization of coated capillaries prevents adsorption of bacteria to the capillary wall. Another approach is utilization of a dilute dissolved polymer, polyethylene oxide (PEO) in the running buffer as a non-bonded coating for the purpose of altering the EOE These experiment have proved the possibility of diagnosing a variety of diseases and the ability to separate and identify viable cells.     

Electrophoretic mobility of human erythrocytes in the presence of poly(styrene sulfonate)

The adsorption and depletion of the anionic polymer poly(styrene sulfonate) (PSS) on fresh human red blood cells (RBC) were investigated by measuring RBC electrophoretic mobility as a function of polymer molecular mass (48-2610 kDa), ionic strength (15 and 150 mM NaCl) and polymer concentration (相似文献   

The formation of non-soluble complexes between polyethyleneimine-anions and their potential use to isolate enzymes

The aqueous solution behavior of polyethyleneimine (a synthetic cationic polymer) in the presence of anions with two or more electrical charges (citrate, phosphate, sulphate, malate, malonate and succinate) was studied by means of turbidimetry and light scattering. Polyethyleneimine forms non-soluble complexes with these anions, which behave as a pseudo-polyampholyte with an isoelectrical pH value dependent on the type of anion. The effect of pH, polymer concentration and ionic strength on the non-soluble complexes formation was examined. The complex precipitation pH range was between 3.5 and 8.0 and also depended on the type of anion. The complex formation was inhibited by the ionic strength in agreement with the electrostatic mechanism of the non-soluble complex formation. Model proteins with isoelectric pH from 1 to 10 were assayed in orden to be precipitated by these complexes. It was found that the non-soluble polyethyleneimine-anion complexes have the property to precipitate macromolecules charged with an opposite electrical charge.     

Investigation of the effect of ionic strength of Tris-acetate background electrolyte on electrophoretic mobilities of mono-, di-, and trivalent organic anions by capillary electrophoresis

The effect of ionic strength of the background electrolyte (BGE) composed of tris(hydroxymethyl)aminomethane (Tris) and acetic acid on the electrophoretic mobility of mono-, di- and trivalent anions of aliphatic and aromatic carboxylic and sulfonic acids was investigated by capillary zone electrophoresis (CZE). Actual ionic mobilities of the above anions were determined from their CZE separations in Tris-acetate BGEs of pH 8.1 to 8.2 in the 3 to 100 mM ionic strength interval at constant temperature (25 degrees C). It was found that the ionic strength dependence of experimentally determined actual ionic mobilities does not follow the course supposed by the classical Onsager theory. A steeper decrease of actual ionic mobilities with the increasing ionic strength of BGE and a higher estimated limiting mobility of the anions than that found in the literature could be attributed to the specific behavior of the Tris-acetate BGEs. Presumably, not only a single type of interaction of anionic analytes with BGE constituents but rather the combination of effects, such as ion association or complexation equilibria, seems to be responsible for the observed deviation of the concentration dependence of the actual ionic mobilities from the Onsager theory. Additionally, several methods for the determination of limiting ionic mobilities from CZE measured actual ionic mobilities were evaluated. It turned out that the determined limiting ionic mobilities significantly depend on the calculation procedure used.     

Determination of the Critical Micelle Concentration of Cationic Surfactants by Capillary Electrophoresis

The determination of the critical micelle concentration (CMC) of cationic surfactants by capillary electrophoresis was demonstrated. In this study, tetradecyltrimethylammonium bromide (TTAB) and dodecyltrimethylammonium bromide (DoTAB) were selected as cationic surfactants and propazine was chosen as test solute. In the evolution of the effective electrophoretic mobility of propazine as a function of surfactant concentration, a dramatic change in slope at a particular concentration is a good indication of the CMC of this surfactant. The CMC values determined experimentally were further confirmed by a curve-fitting approach. Simulation of the electrophoretic mobility curves as a function of surfactant concentration in both micellar electrokinetic chromatography and capillary zone electrophoresis using cationic surfactants as an electrolyte modifier was performed for propazine, and the intersection of these two mobility curves allowed us to precisely predict the CMC of the surfactant. The CMC values determined for TTAB and DoTAB are 1.6 ± 0.1 and 11.0 ± 0.1 mM, respectively, in the case of an electrolytic solution consisting of 70 mM phosphate buffer at pH 6.0. Moreover, the applicability of the electroosmotic mobility as a parameter for the determination of the CMC was examined.     

Nitromethane as solvent in capillary electrophoresis

Nitromethane has several properties that make it an interesting solvent for capillary electrophoresis especially for lipophilic analytes that are not sufficiently soluble in water: freezing and boiling points are suitable for laboratory conditions, low viscosity leads to favourable electrophoretic mobilities, or an intermediate dielectric constant enables dissolution of electrolytes. In the present work we investigate the change of electrophoretically relevant analyte properties - mobilities and pKa values - in nitromethane in dependence on the most important experimental conditions determined by the background electrolyte: the ionic strength, I, and the pH. It was found that the mobility decreases with increasing ionic strength (by, e.g. up to 30% from I = 0 to 50 mmol/L) according to theory. An appropriate pH scale is established by the aid of applying different concentration ratios of a buffer acid with known pKa and its conjugate base. The mobility of the anionic analytes (from weak neutral acids) depends on the pH with the typical sigmoidal curve in accordance with theory. The pKa of neutral acids derived from these curves is shifted by as much as 14 pK units in nitromethane compared to water. Both findings confirm the agreement of the electrophoretic behaviour of the analytes with theories of electrolyte solutions. Separation of several neutral analytes was demonstrated upon formation of charged complexes due to heteroconjugation with chloride as ionic constituent of the background electrolyte.