Formation Of Polyelectrolyte Complexes Research Articles

Complexation of Poly(ethylene glycol)-(ds)OligoDNA Conjugates with Ionic Liquids.

We report the complexation of poly(ethylene glycol) conjugated double-stranded oligoDNA (PEG-(ds)oligoDNA) with imidazolium-based ionic liquids (ILs) to form polyelectrolyte complex aggregates (PCAs). The PEG-(ds)oligoDNA conjugates are prepared following a solution-phase coupling reaction. The binding of PEG-(ds)oligoDNA with either 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]) or 1-hexyl-3-methylimidazolium tetrafluoroborate ([HMIM][BF4]) is confirmed by a fluorescence displacement assay. Both ILs show stronger binding affinity to PEG-(ds)oligoDNA than bare (ds)oligoDNA due to the PEG-assisted increase in IL cation concentration in the vicinity of (ds)oligoDNA. The complex morphology formed at various amine (N) to phosphate (P) ratios is also examined. At high N/P ratios above 4, nanosized PCAs are formed, driven by a counterion-mediated attraction among the IL-bound (ds)oligoDNA segments and stabilized by the conjugated PEG segments. The PCAs exhibit near-neutral surface charges and resistance to DNase degradation, suggesting their potential use in gene delivery applications.

Investigation of Silk Fibroin/Poly(Acrylic Acid) Interactions in Aqueous Solution.

Silk fibroin (SF) is a protein with many outstanding properties (superior biocompatibility, mechanical strength, etc.) and is often used in many advanced applications (epidermal sensors, tissue engineering, etc.). The properties of SF-based biomaterials may additionally be tuned by SF interactions with other (bio)polymers. Being a weak amphoteric polyelectrolyte, SF may form polyelectrolyte complexes (PECs) with other polyelectrolytes of opposite charge, such as poly(acrylic acid) (PAA). PAA is a widely used, biocompatible, synthetic polyanion. Here, we investigate PEC formation between SF and PAA of two different molecular weights (MWs), low and high, using various techniques (turbidimetry, zeta potential measurements, capillary viscometry, and tensiometry). The colloidal properties of SF isolated from Bombyx mori and of PAAs (MW, overlap concentration, the influence of pH on zeta potential, adsorption at air/water interface) were determined to identify conditions for the SF-PAA electrostatic interaction. It was shown that SF-PAA PEC formation takes place at different SF:PAA ratios, at pH 3, for both high and low MW PAA. SF-PAA PEC's properties (phase separation, charge, and surface activity) are influenced by the SF:PAA mass ratio and/or the MW of PAA. The findings on the interactions contribute to the future development of SP-PAA PEC-based films and bioadhesives with tailored properties.

Polyelectrolyte complexes based on a novel and sustainable hemicellulose-rich lignosulphonate for drug delivery applications.

Polyelectrolyte complexes (PECs) are polymeric structures formed by the self-assembly of oppositely charged polymers. Novel biomaterials based on PECs are currently under investigation as drug delivery systems, among other applications. This strategy leverages the ability of PECs to entrap drugs under mild conditions and control their release. In this study, we combined a novel and sustainably produced hemicellulose-rich lignosulphonate polymer (EH, negatively charged) with polyethyleneimine (PEI) or chitosan (CH, positively charged) and agar for the development of drug-releasing PECs. A preliminary screening demonstrated the effect of several parameters (polyelectrolyte ratio, temperature, and type of polycation) on PECs formation. From this, selected formulations were further characterized in terms of thermal properties, surface morphology at the microscale, stability, and ability to load and release methylene blue (MB) as a model drug. EH/PEI complexes had a more pronounced gel-like behaviour compared to the EH/CH complexes. Differential scanning calorimetry (DSC) results supported the establishment of polymeric interactions during complexation. Overall, PECs' stability was positively affected by low pH, ratios close to 1:1, and the addition of agar. PECs with higher EH content showed a higher MB loading, likely promoted by stronger electrostatic interactions. The EH/CH formulation enriched with agar showed the best sustained release profile of MB during the first 30h in a pH-dependent environment simulating the gastrointestinal tract. Overall, we defined the conditions to formulate novel PECs based on a sustainable hemicellulose-rich lignosulphonate for potential applications in drug delivery, which promotes the valuable synergy between sustainability and the biomedical field.

Response Surface Methodology: An Optimization of Process Variables for the Nanoencapsulation of Anthocyanins from Black Rice Bran

Nanoencapsulation technology has been used in food and pharmaceutical applications to increase bioactive chemical functioning and stability against external influences. To develop a cost-effective encapsulating procedure, additional optimization is required. This study employed response surface methodology (RSM) to optimize the encapsulation of anthocyanin-rich extract from black rice bran. The extract was encapsulated through pre-gelation and polyelectrolyte complex formation processes. Box-Behnken design was employed to determine the optimum conditions for the encapsulation process with the following process variables: chitosan concentration, pH, and CaCl2 concentration. Chemical characteristics, surface morphology, and particle size were used to describe the resultant capsules, which were then subjected to phytochemical analysis. The optimal encapsulation conditions for anthocyanin were 6.30 mg/mL chitosan, pH 5.5, and 36 mM CaCl2, with a 51.20 % encapsulation efficiency. The developed anthocyanin-loaded nanocapsule has a high TPC (3.87 mg GAE/g) and potent antioxidant activity (5.69 mg TE/g). SEM images revealed a smooth surface area and spherical particles that clumped together, with an average particle size of 94.70 nm. FTIR analysis corroborates the well-incorporation of anthocyanin into the nanocapsules. The encapsulation process of anthocyanin-rich extract from black rice bran was successfully optimized via RSM.

Additive manufacturing of wet-spun chitosan/hyaluronic acid scaffolds for biomedical applications

Additive manufacturing (AM) holds great potential for processing natural polymer hydrogels into 3D scaffolds exploitable for tissue engineering and in vitro tissue modelling. The aim of this research activity was to assess the suitability of computer-aided wet-spinning (CAWS) for AM of hyaluronic acid (HA)/chitosan (Cs) polyelectrolyte complex (PEC) hydrogels. A post-printing treatment based on HA chemical cross-linking via transesterification with poly(methyl vinyl ether-alt-maleic acid) (PMVEMA) was investigated to enhance the structural stability of the developed scaffolds in physiological conditions. PEC formation and the esterification reaction were investigated by infrared spectroscopy, thermogravimetric analysis, evolved gas analysis-mass spectrometry, and differential scanning calorimetry measurements. In addition, variation of PMVEMA concentration in the cross-linking medium was demonstrated to strongly influence scaffold water uptake and its stability in phosphate buffer saline at 37 °C. The in vitro cytocompatibility of the developed hydrogels was demonstrated by employing the murine embryo fibroblast Balb/3T3 clone A31 cell line, highlighting that PMVEMA cross-linking improved scaffold cell colonization. The results achieved demonstrated that the developed hydrogels represent suitable 3D scaffolds for long term cell culture experiments.

Polyelectrolyte-Complex-Based Hydrogel Inserts for Vaginal Delivery of Posaconazole and Probiotics.

Worldwide, 40 to 50% of women suffer from reproductive tract infections. Most of these infections are mixed infections, are recurrent and difficult to treat with antimicrobials or antifungals alone. For symptomatic relief of infections, oral antimicrobial therapy must be combined with topical therapy. The purpose of this work is to optimize and develop a polyelectrolyte complex (PEC) of chitosan/anion for the formulation of posaconazole- and probiotic-loaded vaginal hydrogel inserts with prolonged release and significant mucoadhesion. PECs were prepared using chitosan as cationic and carrageenan, pectin and polycarbophil as anionic polymers via a lyophilization technique. PEC formation was confirmed by scanning electron microscopy, Fourier transform infrared spectroscopy and differential scanning calorimetry, by observing changes in its surface, physical and thermal properties. The probiotic, Lactobacillus casei, was added to the PEC during the lyophilization process and the effect on the probiotic viability was studied. The PECs were further compressed along with posaconazole to form hydrogel inserts and optimized using a 32 full-factorial design. The hydrogel inserts were assessed for swelling behavior, drug release, in vitro mucoadhesion and in vitro antifungal activity. The chitosan-pectin hydrogel insert demonstrated excellent mucoadhesion (1.25 N), sustained drug release (88.2 ± 2.4% in 8 h) and a swelling index of 154.7%. The efficacy of hydrogel inserts was evaluated using in vitro study with a co-culture of Lactobacillus casei and Candida albicans. This study revealed an increase in Lactobacilli casei count and a significant drop in the viable count of Candida albicans (4-log reduction in 24 h), indicating the effectiveness of hydrogel inserts in alleviating the fungal infection. Overall, our study demonstrated the potential of the hydrogel insert for preventing vaginal infection and restoring normal vaginal microbiota.

Instantaneous and reversible flocculation of Scenedesmus via Chitosan and Xanthan Gum complexation

An instantaneous and reversible flocculation method for Scenedesmus harvesting was developed, based on the complexation of Chitosan (CTS) and Xanthan Gum (XG). Under rapid stirring, Scenedesmus cells formed centimeter-sized flocs within 20 s using binary flocculants of 4 mg/L CTS and 16 mg/L XG. These flocs exhibited a remarkable harvest efficiency exceeding 95 % when filtered through 500-μm-pore-sized sieves. Furthermore, the flocs could be completely disintegrated by using alkaline or NaCl solutions (pH > 11 or NaCl concentration > 1.5 mol/L). Adjusting pH allowed recovery of 50 % CTS and 75 % XG, resulting in microalgae biomass with lower flocculant content and reducing reagent costs. Electrostatic interaction of –COO– of XG and –NH3+ of CTS deduced the formation of polyelectrolyte complexes (PECs), which shrink and wrap the coexisting algal cells to form the flocs under stirring. CTS and XG complexation was instantaneous and reversible, explaining quick flocculation and disintegration.

Design, Development, and In vitro Evaluation of Single Unit Hydrodynamically Balanced System of Captopril

Background: This study investigated the use of in situ polyelectrolyte complex formation by using two oppositely charged polysaccharides [Chitosan (cationic), Sodium Alginate (anionic)]. It forms 3-D intercalation and interpenetrating network helping in controlling the release of highly acid-soluble Captopril. Objective: To develop a polyelectrolyte complex based single unit gastroretentive tablet by using optimization based 3 (2) Taguchi factorial design for controlled delivery of Captopril. Materials and Methods: Gastroretentive Captopril tablets were prepared by the direct compression technique. Total 09 batches were prepared as per 3 (2) Taguchi factorial design studies of 100 tablets each. Results: Thermal analysis method revealed that there is a formation of PEC between chitosan and sodium alginate. In vitro buoyancy and T60%, drug release studies revealed that due to complex formation, formulation remains stable and remains buoyant. From factorial design studies, it was interpreted that for buoyancy time (Y1) chitosan desired effect value was found higher. For 60% drug release (T60%; Y2) both chitosan and sodium alginate have a synergistic effect. Durbin Watson's statistical model and residual data suggested that the model is statistically validated. All formulations follow the zero-order kinetics. Stability studies revealed that formulations F5 and F9 remain stable for long-term stability studies without showing any significant changes. The fit analysis studies indicated that the prepared formulation was different from the innovator product indicating low f1 and f2 values. Conclusion: From the result generated it was concluded that chitosan-sodium alginate polyelectrolyte complex has sufficient potential to retard the release of CPT.

Ascorbic acid nanoencapsulation using polyelectrolyte complex formation and optimization using hybrid artificial neural network‐genetic algorithm

AbstractBackgroundsThe polyelectrolyte complex (PEC) formation using chitosan (Cs) and alginate (Alg) has been employed to carry out Vitamin C (VC) nanoencapsulation because of its instability in adverse conditions. This method includes VC nanoencapsulation using physical cross‐linking. The effect of the mixing order as well as the different mass ratios of both the polymer and the VC content, were investigated on the size, pdi, zeta potential, encapsulation efficiency (EE%), and yield%. Hence, considering different mass ratios of both polymer (4:1–1:4) and VC content (10%–30% w/w of Cs) as independent variables, PECs were formed using 0.1% (w/v) of Cs and Alg solution.ResultThe result showed that, for equal mass ratio (1:1) of Cs and Alg, the addition of Alg solution to Cs solution led to lower particle size, while higher particle size was observed with reverse order of addition. However, no significant effect of polymer mass ratios was observed on particle size and NPs stability, while EE varied with VC concentration. Artificial neural network (ANN) was applied to train the experimental parameters Cs: Alg ratios (X1:X2) and VC content (X3) for the output variables. Moreover, process optimization was carried out using multi‐objective genetic algorithm (MOGA) with the goal of lowering particle size and increasing EE while increasing nanoparticle yield.ConclusionThe PEC method effectively encapsulated VC as obtained from higher EE. The Cs: Alg ratio of 4:2.1 and 18% VC content (w/w of Cs) was found optimum for nanoencapsulation. The final ANN‐GA model showed an acceptable agreement with experimental data.

Effect of ScCO2 on the decontamination of PECs-based cryogels: A comparison with H2O steam and H2O2 nebulization methods

Biopolymers present ideal properties to be used in wound dressing solutions. By mixing two oppositely charged macromolecules it is possible to form polyelectrolyte complex (PEC) based cryogels using lyophilization. Their application in the biomedical field is limited due to their sterilization requirements, as conventional methods compromise their physicochemical properties. ScCO2 appears as an alternative method for decontamination. This work assessed several cryogel PEC formulations, chitosan-pectin, gelatine-xanthan gum and alginate-gelatine. PEC formation was confirmed by FTIR and rheological analysis. While steam sterilization compromised cryogels’ chemical and morphological properties, decontamination with scCO2 proved to be a promising method for decontamination of PEC-cryogels, because, similarly to what is observed with hydrogen peroxide, it does not compromise their physicochemical properties.

Taste-Masked Flucloxacillin Powder Part 2: Formulation Optimisation Using the Mixture Design Approach and Storage Stability.

Flucloxacillin is prescribed to treat skin infections but its highly bitter taste is poorly tolerated in children. This work describes the application of the D-optimal mixture experimental design to identify the optimal component ratio of flucloxacillin, Eudragit EPO and palmitic acid to prepare flucloxacillin taste-masked microparticles that would be stable to storage and would inhibit flucloxacillin release in the oral cavity while facilitating the total release of the flucloxacillin load in the lower gastrointestinal tract (GIT). The model predicted ratio was found to be very close to the stoichiometric equimolar component ratio, which supported our hypothesis that the ionic interactions among flucloxacillin, Eudragit EPO and palmitic acid underscore the polyelectrolyte complex formation in the flucloxacillin taste-masked microparticles. The excipient-drug interactions showed protective effects on the microparticle storage stability and minimised flucloxacillin release at 2 min in dissolution medium. These interactions had less influence on flucloxacillin release in the dissolution medium at 60 min. Storage temperature and relative humidity significantly affected the chemical stability of the microparticles. At the preferred storage conditions of ambient temperature under reduced RH of 23%, over 90% of the baseline drug load was retained in the microparticles at 12 months of storage.

ZnO Nanoparticles-Reinforced Chitosan-Xanthan Gum Blend Novel Film with Enhanced Properties and Degradability for Application in Food Packaging.

Nations all over the world are imposing ban on single-use plastics, which are difficult to recycle and lead to creations of nonsustainable and nondegradable piles. To match the requirement in the market, suitable food packaging alternatives have to be developed that are biodegradable and environment-friendly. The current work is designed for the fabrication of a novel nanocomposite by blending xanthan gum in a chitosan matrix and reinforcing it with ZnO nanoparticles, through a solution casting method. Surface morphology of the film was investigated through field emission scanning electron microscopy, along with energy-dispersive X-ray spectroscopy mapping, and characterized through thermogravimetric analysis, Fourier transform infrared (FTIR) spectroscopy, mechanical testing, and ultraviolet spectroscopy. FTIR spectroscopy analysis corroborated the interaction between the components and the H-bond formation. Polyelectrolyte complex formation materializes between the oppositely charged chitosan and xanthan gum, and further nanoparticle incorporation significantly improves the mechanical properties. The synthesized nanocomposite was found to have increases in the tensile strength and elongation at break of pure chitosan by up to 6.65 and 3.57 times, respectively. The transmittance percentage of the bionanocomposite film was reduced compared to that of the pure chitosan film, which aids in lowering the oxidative damage brought on by UV radiation in packed food products. Moreover, the film also showed an enhanced barrier property against water vapor and oxygen gas. The film was totally biodegradable in soil burial at the end of the second month; it lost almost around 88% of its initial weight. The fabricated film does not pose a threat to the environment and hence has great potential for application in the future sustainable food packaging industry.

Use of Chitosan-Based Polyelectrolyte Complexes for Its Potential Application in Active Food Packaging: A Review of Recent Literature.

The current challenges in the food packaging field are, on one side, replacing plastic from non-renewable sources with biopolymers and, on the other hand, generating a packaging material with attractive properties for the consumer. Currently, the consumer is ecologically concerned; the food packaging industry must think ahead to satisfy their needs. In this context, the utilization of polyelectrolyte complexes (PECs) in this industry presents itself as an excellent candidate for fulfilling these requirements. PECs possess enticing characteristics such as encapsulation, protection, and transportation, among others. On the other hand, diverse types of biopolymers have been used in the formation of PECs, such as alginate, cellulose, gelatin, collagen, and so on. Hence, this paper reviews the use of PECs in food packaging where chitosan forms polyelectrolyte complexes.

Complexation between chitosan and carboxymethyl cellulose in weakly acidic, neutral, and weakly alcaline media

The interaction between carboxymethyl cellulose and partially reacetylated chitosan soluble in acidic and alkaline aqueous media is studied by light scattering and isothermal titration calorimetry in a wide pH range. It is shown that the formation of polyelectrolyte complexes (PEC) can occur in the pH range of 6–8, while this pair of polyelectrolytes loses the ability to complexation upon transition to a more alkaline medium. The revealed dependence of the observed enthalpy of interaction on the ionization enthalpy of the buffer indicates the participation of proton transfer from the buffer substance to chitosan and its additional ionization in the binding process. This phenomenon is first observed in a mixture of a weak polybase chitosan and a weak polyacid. The possibility to obtain soluble nonstoichiometric PEC by a direct mixing of the components in a weakly alkaline medium is shown. The resulting PECs are polymolecular particles in shape close to homogeneous spheres with a radius of about 100 nm. The obtained results are promising for creating of biocompatible and biodegradable drug delivery systems.

Effects of Salt on Phase Behavior and Rheological Properties of Alginate-Chitosan Polyelectrolyte Complexes.

Oppositely charged polyelectrolytes often form polyelectrolyte complexes (PECs) due to the association through electrostatic interactions. Obtaining PECs using natural, biocompatible polyelectrolytes is of interest in the food, pharmaceutical, and biomedical industries. In this work, PECs were prepared from two biopolymers, positively charged chitosan and negatively charged alginate. We investigate the changes in the structure and properties of PECs by adding sodium chloride (salt doping) to the system. The shear modulus of PECs can be tuned from ∼10 to 104 Pa by changing the salt concentration. The addition of salt led to a decrease in the water content of the complex phase with increasing shear modulus. However, at a very high salt concentration, the shear modulus of the complex phase decreased but did not lead to the liquid coacervate formation, typical of synthetic polyelectrolytes. This difference in phase behavior has likely been attributed to the hydrophobicity of chitosan and long semiflexible alginate and chitosan chains that restrict the conformational changes. Large amplitude oscillatory shear experiments captured nonlinear responses of PECs. The compositions of the PECs, determined as a function of salt concentration, signify the preferential partitioning of salt into the complex phase. Small-angle X-ray scattering of the salt-doped PECs indicates that the Kuhn length and radius of the alginate-chitosan associated structure qualitatively agree with the captured phase behavior and rheological data. This study provides insights into the structure-property as a function of salt concentration of natural polymer-based PECs necessary for developing functional materials from natural polyelectrolytes.

Development of PEG-grafted-lignosulfonate/cationic-polyelectrolyte/poly(acrylic acid) complex and evaluation of its toughness, self-healing property, and internal physical structure

A lignosulfonate-derived material was prepared by complexing polyethylene glycol (PEG)-grafted lignosulfonate (LS-g-PEG) with a cationic polyelectrolyte (PDADMACl). The mechanical property of this LS-g-PEG/PDADMACl complex was similar to those of the conventional unmodified-LS/PDADMACl complex, however, the addition of poly(acrylic acid) (PAAc) improved the toughness of the LS-g-PEG complex more than seven-fold at the optimal composition (from 0.7 to 5.2 MJ/m3). This increase in toughness upon PAAc addition was not observed in the conventional unmodified-LS/PDADMACl complex and it was attributed to the synergistic effect of plasticization by the amorphous PEG component, as well as the formation of a rigid polyelectrolyte complex. In addition to better strain and toughness than other reported lignosulfonate-derived materials, the LS-g-PEG/PDADMACl/PAAc complex displayed a humidity-induced self-healing property; complete healing of mechanical properties was observed under optimal conditions. These good toughness and excellent self-healing properties may broaden the applications of lignin-derived materials as highly durable and damage-resistant materials.

On the Fractionation and Physicochemical Characterisation of Self-Assembled Chitosan-DNA Polyelectrolyte Complexes.

Chitosan is extensively studied as a carrier for gene delivery and is an attractive non-viral gene vector owing to its polycationic, biodegradable, and biocompatible nature. Thus, it is essential to understand the chemistry of self-assembled chitosan-DNA complexation and their structural and functional properties, enabling the formation of an effective non-viral gene delivery system. In this study, two parent chitosans (samples NAS-032 and NAS-075; Mw range ~118-164 kDa) and their depolymerised derivatives (deploy nas-032 and deploy nas-075; Mw range 6-14 kDa) with degrees of acetylation 43.4 and 4.7%, respectively, were used to form polyelectrolyte complexes (PECs) with DNA at varying [-NH3+]/[-PO4-] (N/P) molar charge ratios. We investigated the formation of the PECs using ζ-potential, asymmetric flow field-flow fractionation (AF4) coupled with multiangle light scattering (MALS), refractive index (RI), ultraviolet (UV) and dynamic light scattering (DLS) detectors, and TEM imaging. PEC formation was confirmed by ζ-potential measurements that shifted from negative to positive values at N/P ratio ~2. The radius of gyration (Rg) was determined for the eluting fractions by AF4-MALS-RI-UV, while the corresponding hydrodynamic radius (Rh), by the DLS data. We studied the influence of different cross-flow rates on AF4 elution patterns for PECs obtained at N/P ratios 5, 10, and 20. The determined rho shape factor (ρ = Rg/Rh) values for the various PECs corresponded with a sphere morphology (ρ ~0.77-0.85), which was consistent with TEM images. The results of this study represent a further step towards the characterisation of chitosan-DNA PECs by the use of multi-detection AF4 as an important tool to fractionate and infer aspects of their morphology.

Physicochemical Properties and Antiherpetic Activity of κ-Carrageenan Complex with Chitosan.

Nanoparticles formation is one of the ways to modulate the physicochemical properties and enhance the activity of original polysaccharides. For this purpose, based on the polysaccharide of red algae, κ-carrageenan (κ-CRG), it polyelectrolyte complex (PEC), with chitosan, were obtained. The complex formation was confirmed by ultracentrifugation in a Percoll gradient, with dynamic light scattering. According to electron microscopy and DLS, PEC is dense spherical particles with sizes in the range of 150-250 nm. A decrease in the polydispersity of the initial CRG was detected after the PEC formation. Simultaneous exposure of Vero cells with the studied compounds and herpes simplex virus type 1 (HSV-1) showed that the PEC exhibited significant antiviral activity, effectively inhibiting the early stages of virus-cell interaction. A two-fold increase in the antiherpetic activity (selective index) of PEC compared to κ-CRG was shown, which may be due to a change in the physicochemical characteristics of κ-CRG in PEC.

Polysaccharide-based polyampholyte complex formation: Investigating the role of intra-chain interactions

The difference in inter-chain and intra-chain electrostatic attraction was investigated in polyelectrolyte and polyampholyte electrostatic complex formation. Three polymers with similar backbone molecular structures including chitosan (Ch) polycation, carboxymethyl cellulose (CMCe) polyanion, and carboxymethyl chitosan (CMCh) polyampholyte were used for this purpose. The turbidimetric, water content, and rheological measurements for polyampholyte self-complex showed more dependence on the ionic strength rather than the polyelectrolyte one. The degree of dissociation (α), dissociation constant (pKa), and intrinsic persistence length were calculated by applying the Katchalsky-Lifson model to potentiometric data. We studied the gyration radii as a function of Debye length and observed the polyampholyte chain contractions due to the intra-chain electrostatic attractions, which minimize the entropic gain of the inter-chain complex formation. This is in accordance with the decrease in pKa by αc for CMCh which is the opposite of that for the Ch and CMCe samples. We also found that the polyampholyte has less intrinsic and electrostatic persistence length compared with both polyanion and polycation with similar chain structures indicating the impact of the inter-chain electrostatic interaction on the complex properties. This study deepens our insight about the behavior of CMCh and the nature of difference between CMCh and Ch/CMCe electrostatic complexes.

Nanoparticle forming polyelectrolyte complexes derived from well-defined block copolymers

Polymers can be used in nanoparticle associated formulations to encapsulate cytotoxic drugs (e.g., paclitaxel). Polyelectrolyte complexes (PECs) that form drug associated colloids also have potential to form particulate associated formulations. We used RAFT polymerisation to prepare small families of narrow molecular weight distributed (i) methacrylate block co-polymers comprised of oligomeric ethylene glycol, poly(ethylene glycol) methyl ether methacrylate (PEGMA), and dimethyl amino pendent chains, 2-(dimethylamino) ethyl methacrylate (DMAEMA), and (ii) poly(methacrylic acid), PMAA. These polymers were examined for their ability to form PECs capable of drug encapsulation. Optimal control in RAFT polymerisation was confirmed by the linear increase of molecular weight and the narrow dispersity of the polymers (<1.2) as determined by 1H nuclear magnetic resonance and gel permeation chromatography. Dynamic light scattering and transmission electron microscopy showed formation of well-defined monodispersed nanoparticles with a hydrodynamic diameter of 25 ± 3 nm upon self-assembly of poly(PEGMA0.23-b-DMAEMA0.77)99 and PMAA75. These PECs are highly haemocompatible. Thin film hydration was used to encapsulate two hydrophobic drugs, paclitaxel and carmofur, into spherical nanoparticles. The results show that carmofur was encapsulated markedly more effectively than paclitaxel (72 vs 1.5%).