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PubMedDate not supplied

Formation of polyelectrolyte complex particles from self-complexation of N-sulfated chitosan.

This work investigated the elaboration of biocompatible nanoparticles from the pH-induced self-complexation of the amphoteric polysaccharide N-sulfated chitosan. The acidification of aqueous solutions of chitosan having a degree of acetylation of 24% and a degree of sulfation of 34% or 56% was followed stepwise by turbidimetry, dynamic light scattering, and electrophoresis. With the highest sulfated chitosan, no turbidity was recorded between pH = 7.8 and 2.0, traducing a high apparent solubility of the polymer chains in this domain of pH. With the lowest sulfated chitosan, a steady increase in turbidity was monitored from pH = 6.90 to 6.15 followed by the flocculation of the polymer at pH approximately 6.0. In this range of pH, the polymer phase separated to yield particles having hydrodynamic diameters decreasing from 350 to 260 nm and an almost constant negative charge. These particles were assembled by electrostatic interactions between the protonated amino residues and the sulfate functions and stabilized by an excess of surface sulfate groups. The particles could be separated from the reaction medium and concentrated by centrifugation-redispersion cycles without alteration of their structure.

Chitosan↗
PubMedDate not supplied

Influence of chitosan structure on the formation and stability of DNA-chitosan polyelectrolyte complexes.

The interactions between DNA and chitosans varying in fractional content of acetylated units (FA), degree of polymerization (DP), and degree of ionization were investigated by several techniques, including an ethidium bromide (EtBr) fluorescence assay, gel retardation, atomic force microscopy, and dynamic and electrophoretic light scattering. The charge density of the chitosan and the number of charges per chain were found to be the dominating factors for the structure and stability of DNA-chitosan complexes. All high molecular weight chitosans condensed DNA into physically stable polyplexes; however, the properties of the complexes were strongly dependent on FA, and thereby the charge density of chitosan. By employing fully charged oligomers of constant charge density, it was shown that the complexation of DNA and stability of the polyplexes is governed by the number of cationic residues per chain. A minimum of 6-9 positive charges appeared necessary to provide interaction strength comparable to that of polycations. In contrast, further increase in the number of charges above 9 did not increase the apparent binding affinity as judged from the EtBr displacement assay. The chitosan oligomers exhibited a pH-dependent interaction with DNA, reflecting the number of ionized amino groups. The complexation of DNA and the stability of oligomer-based polyplexes became reduced above pH 7.4. Such pH-dependent dissociation of polyplexes around the physiological pH is highly relevant in gene delivery applications and might be one of the reasons for the high transfection activity of oligomer-based polyplexes observed.

Animals↗
PubMed2006

Effects of polyelectrolyte chain stiffness, charge mobility, and charge sequences on binding to proteins and micelles.

The binding affinities of polyanions for bovine serum albumin in NaCl solutions from I = 0.01-0.6 M, were evaluated on the basis of the pH at the point of incipient binding, converting each such pH(c) value into a critical protein charge Zc. Analogous values of critical charge for mixed micelles were obtained as the cationic surfactant mole fraction Yc. The data were well fitted as Yc or Zc = KI a, and values of K and a were considered as a function of normalized polymer charge densities (tau), charge mobility, and chain stiffness. Binding increased with chain flexibility and charge mobility, as expected from simulations and theory. Complex effects of tau were related to intrapolyanion repulsions within micelle-bound loops (seen in the simulations) or negative protein domain-polyanion repulsions. The linearity of Zc with radicalI at I < 0.3 M was explained by using protein electrostatic images, showing that Zc at I < 0.3 M depends on a single positive "patch"; the appearance of multiple positive domains I > 0.3 M (lower pH(c)) disrupts this simple behavior.

Animals↗
PubMed2006

Polyelectrolyte study of the calcium-induced chain association of pectate.

The theoretical model devised in the previous paper (Donati, I.; Benegas, J. C.; Cesàro, A.; Paoletti, S. Biomacromolecules 2006, 7 (5), 1587-1596) for the description of ion-induced chain aggregation is here applied to the case of chain dimerization of poly(galacturonate) in the presence of calcium ions. Particular attention has been directed toward the initial stage of dimer formation [i.e., in the low regime of calcium-to-polymer ratio (Rj)]. Circular dichroism (CD) data allowed evaluation of the fraction, theta, of calcium ions bound within chain dimers according to the "egg-box"-model. The theoretical model was able to reproduce satisfactorily the total molar enthalpy variation experimentally determined; the contributions of affinity (specificity in territorial condensation) and chemical bonding of calcium counterions to the thermodynamic properties of the system (i.e., enthalpy and entropy) were calculated. The intrinsic molar enthalpy of bonding, DeltaH(bond,0), displayed a peculiar sigmoid dependence on Rj. In particular, its decrease toward more negative values was interpreted as stemming from a (cooperative) calcium-induced conformational change that accompanies pectate chain pairing upon junction formation. The calculated pKin of instability of the Ca-(GalA-)4 complex was 10.80, in very good agreement with the corresponding value reported for the Ca-EDTA complex (i.e., 10.96). Significant contributions to the complex stability were the enthalpy of ion pairing (DeltaH(ionpairing,bond) = -5.1 kcal (mol calcium)-1, in good agreement with the value reported for calcium-EDTA: approximately -5.4 kcal (mol calcium)-1), and the entropy of desolvation (DeltaS(desolv,bond) = 43.7 cal mol-1 K-1, well within the range of values reported for calcium-EDTA: 42-57 cal mol-1 K-1).

Calcium↗
PubMed2006

Adhesion of polyelectrolyte microcapsules through biotin-streptavidin specific interaction.

Adhesion of PAH/PSS and PDADMAC/PSS capsules through electrostatic and specific interactions has been investigated using reflective interference contrast microscopy (RICM). Adhesion of capsules via electrostatic interactions was found to be spontaneous and strong. Capsules functionalized with poly(l-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG) did not exhibit significant adhesion (as determined by the adhesion area) to streptavidin-coated substrates, whereas capsules functionalized with biotinylated PLL-g-PEG showed a significantly larger adhesion area. Using continuum mechanical models, the total adhesion energies for these cases were calculated and were found to correspond to several tens of individual biotin-streptavidin pairs. The application of specific interactions such as the biotin-streptavidin system for controlled capsule adhesion has been demonstrated in this study.

Adhesiveness↗
PubMed2006

Polyelectrolyte films based on polysaccharides of different conformations: effects on multilayer structure and mechanical properties.

Ultrathin films were prepared with cationic poly(allylamine hydrochloride) (PAH) and two anionic polysaccharides, iota- and lambda-carrageenan, of similar chemical composition but different conformations using the layer-by-layer (LbL) technique. The study of aqueous solutions of carrageenans confirms that iota-carrageenan is at room temperature in helical conformation while lambda-carrageenan is in random coil conformation. Characterization of the multilayers by ellipsometry, circular dichroism, and AFM revealed that iota-carrageenan keeps its helical conformation within the films while lambda-carrageenan chains are in random coil conformation. Investigation of the mechanical properties of the films by performing nanoindentation experiments using force spectroscopy showed clear differences between the two films based on carrageenans of different conformations.

Carbohydrate Conformation↗
PubMed2000

pH-induced coacervation in complexes of bovine serum albumin and cationic polyelectrolytes.

Turbidity and light scattering measurements, along with phase contrast microscopy, were used to follow the processes leading to coacervation when aqueous solutions of bovine serum albumin (BSA) and poly-(dimethyldiallylammonium chloride) (PDADMAC) were brought from pH = 4 to 10. The state of macromolecular assembly of complexes formed between BSA and PDADMAC prior to and during the pH-induced coacervation could be characterized by specific pH values at which recognizable transitions took place. In addition to the two characteristic pH values (pHcrit and pH phi) previously identified through turbidimetry, other transitions were explicitly established. On the basis of the pH-induced evolution of scattering intensity measurements, we concluded that the formation of soluble primary protein-polymer complexes is initiated at pHcrit and proceeds until "pH'crit". A subsequent increase in scattering intensity at "pHpre" may arise from the assembly of quasi-neutralized primary complexes as their net positive charge decreases with increase in pH. Subsequently, a maximum in scattering intensity at pH phi is observed coincident with the appearance of turbidity and also corresponding to the first microscopic observation of coacervate droplets. The temperature independence of pHcrit and pH phi suggests that hydrophobic contributions are negligible for the initial BSA-PDADMAC interactions and the subsequent coacervation process. The pH dependence of scattering intensity profiles allowed the identification of two other transitions beyond pH phi. Spherical microcoacervate droplets first observed around pH phi subsequently displayed morphological changes at "pHmorph", followed by the transformation to solid or flocculant substances at pHprecip.

Animals↗