Polyelectrolyte Nanocomposites Research Articles

Enhanced drug delivery and wound healing potential of berberine-loaded chitosan-alginate nanocomposite gel: characterization and in vivo assessment.

Berberine-encapsulated polyelectrolyte nanocomposite (BR-PolyET-NC) gel was developed as a long-acting improved wound healing therapy. BR-PolyET-NC was developed using an ionic gelation/complexation method and thereafter loaded into Carbopol gel. Formulation was optimized using Design-Expert® software implementing a three-level, three-factor Box Behnken design (BBD). The concentrations of polymers, namely, chitosan and alginate, and calcium chloride were investigated based on particle size and %EE. Moreover, formulation characterized in vitro for biopharmaceutical performances and their wound healing potency was evaluated in vivo in adult BALB/c mice. The particle distribution analysis showed a nanocomposite size of 71 ± 3.5 nm, polydispersity index (PDI) of 0.45, ζ-potential of +22 mV, BR entrapment of 91 ± 1.6%, and loading efficiency of 12.5 ± 0.91%. Percentage drug release was recorded as 89.50 ± 6.9% with pH 6.8, thereby simulating the wound microenvironment. The in vitro investigation of the nanocomposite gel revealed uniform consistency, well spreadability, and extrudability, which are ideal for topical wound use. The analytical estimation executed using FT-IR, DSC, and X-ray diffraction (XRD) indicated successful formulation with no drug excipients and without the amorphous state. The colony count of microbes was greatly reduced in the BR-PolyET-NC treated group on the 15th day from up to 6 CFU compared to 20 CFU observed in the BR gel treated group. The numbers of monocytes and lymphocytes counts were significantly reduced following healing progression, which reached to a peak level and vanished on the 15th day. The observed experimental characterization and in vivo study indicated the effectiveness of the developed BR-PolyET-NC gel toward wound closure and healing process, and it was found that >99% of the wound closed by 15th day, stimulated via various anti-inflammatory and angiogenic factors.

Self-Healing Iron Oxide Polyelectrolyte Nanocomposites: Influence of Particle Agglomeration and Water on Mechanical Properties

Self-healing nanocomposites can be generated by organic functionalization of inorganic nanoparticles and complementary functionalization of the polymer matrix, allowing reversible interactions between the two components. Here, we report on self-healing nanocomposites based on ionic interactions between anionic copolymers consisting of di(ethylene glycol) methyl ether methacrylate, sodium 4-(methacryloyloxy)butan-1-sulfonate, and cationically functionalized iron oxide nanoparticles. The materials exhibited hygroscopic behavior. At water contents < 6%, the shear modulus was reduced by up to 90%. The nanoparticle concentration was identified as a second factor strongly influencing the mechanical properties of the materials. Backscattered scanning electron microscopy and small-angle X-ray scattering measurements showed the formation of agglomerates in the size range of 100 nm to a few µm in diameter, independent of concentration, resulting in the disordering of the semi-crystalline ionic polymer blocks. These effects resulted in an increase in the shear modulus of the composite from 3.7 MPa to 5.6 MPa, 6.3 Mpa, and 7.5 MPa for 2, 10, and 20 wt% particles, respectively. Temperature-induced self-healing was possible for all composites investigated. However, only 36% of the maximum stress could be recovered in systems with a low nanoparticle content, whereas the original properties were largely restored (>85%) at higher particle contents.

Polyelectrolyte/Graphene Oxide Nano-Film Integrated Fiber-Optic Sensors for High-Sensitive and Rapid-Response Humidity Measurement.

Optical fiber humidity sensors have sparked enormous interests in many fields because of their excellent features. However, it remains a great challenge to balance sensitivity, humidity response, temperature crosstalk, and wet hysteresis for real-world application. To overcome this trade-off, an optical fiber humidity sensor is developed here by coating functional graphene oxide (GO)/polyelectrolyte nanocomposite film on the excessively tilted fiber grating (ex-TFG), in which GO/polyelectrolyte nanocomposite film is employed for enhancing the hydrophilicity and accelerating the adsorption/desorption of water molecule, while the ex-TFG is utilized for improving the sensitivity of refractive index and eliminating the crosstalk of temperature. By this design, optical fiber humidity sensors achieve high sensitivity, rapid response and recovery, low hysteresis, and temperature crosstalk as well as excellent repeatability and stability in large relative humidity (RH) range. Our work provides a promising platform for effective RH monitoring systems that can be widely applied in rapid diagnostics, pharmacy, precision medicine, and so forth.

In-situ growth and characterization of metal oxide nanoparticles within block-copolymer polyelectrolyte membranes

In-situ growth of nanometer size metal oxide crystallites within polyelectrolyte block-copolymer membranes is demonstrated with example of ZnO loaded Nexar and SEBS films. The proposed method allows for the controlled synthesis of ZnO nanoparticles ranging from 2 to 8 nm uniformly dispersed within the membranes. The fabricated films are characterized with XRD, TEM and HAADF-STEM techniques. It is shown that particles size and shape can be tuned by varying the solvent composition. Addition of methanol favors the growth of smaller-sized ZnO. The proposed method can be applied to produce other metal oxide – polyelectrolyte nanocomposites, which may find various applications ranging from fuel cells and other electrochemical devices to separation membranes and protective barriers.

Coagulation performance of cationic polyelectrolyte/TiO2 nanocomposites prepared under LED irradiation

AbstractA series of acrylic‐based cationic polyelectrolyte nanocomposites including water‐soluble monomers acrylamide (AAm) and 2‐acryloyloxyethyltrimethylammonium chloride (DAC) with different mole percent of DAC (30, 40, and 45%) in feed were produced using TiO2 nanoparticles (0.018, 0.037, and 0.11 wt%) as photoinitiator in the aqueous solution of monomers and named as p(ADT)1–9. The LED light at 365 nm was used for photocatalysis activation of TiO2 nanoparticles. Structure and morphology of the synthetic polyelectrolyte were characterized by FT‐IR, NMR, TGA, FESEM‐EDX, and TEM. The other properties of synthetic polyelectrolyte such as molecular weight, viscosity, charge density, AAm/DAC molar ratio in copolymers, reactivity ratio values for the AAm and DAC monomers, and polymerization degree were measured. Furthermore, coagulation performance of these polyelectrolytes was investigated in soil suspension (1,000 ml, initial turbidity = 1,715 NTU). The prepared nanocomposites enhanced the coagulation of soil suspension up to 99.5% in low dosages. The best turbidity removal efficiencies (TRE) between 99.5–99.77% were achieved by p(ADT)3 conatining 30% DAC and 0.11 wt% TiO2. Decreasing the temperature from room temperature to 0°C led to an increase in TRE from 98 to 99.8%. Also, increasing the pH from 4 to 12 led to a decrease in TRE from 99.86 to 94%.

Graphene oxide based functionalized chitosan polyelectrolyte nanocomposite for targeted and pH responsive drug delivery

Graphene oxide (GO) was first modified to amine functionalized GO (AGO) and acts as a cationic polyelectrolyte. Chitosan (CS) was conjugated with folic acid (FA) through N, N´ -Dicyclohexylcarbodiimide coupling to form FA-CS. After this, itaconic acid and acrylic acid monomers are grafted to the hydroxyl group of CS using ethyleneglycol dimethacrylate as cross linker and potassium peroxydisulfate as an initiator to generate –COOH functional groups and forming chemically modified chitosan (CMCS). Further doxorubicin (DOX) loaded into the FA-CMCS/AGO through π-π stacking interactions. The resulting nanocomposite was characterized by FTIR, SEM, TEM, Raman, AFM, DLS and ZP. The drug loading capacity was as high as 95.0% and the drug release rate at pH 5.3 was significantly higher than that under physiological conditions of pH 7.4. Cell viability of L929, HeLa and MCF7 cells was studied. The studies suggest the drug carrier has potential clinical applications for anticancer drug delivery.

Complex Polysaccharide-Based Nanocomposites for Oral Insulin Delivery.

Polyelectrolyte nanocomposites rarely reach a stable state and aggregation often occurs. Here, we report the synthesis of nanocomposites for the oral delivery of insulin composed of alginate, dextran sulfate, poly-(ethylene glycol) 4000, poloxamer 188, chitosan, and bovine serum albumin. The nanocomposites were obtained by Ca2+-induced gelation of alginate followed by an electrostatic-interaction process among the polyelectrolytes. Chitosan seemed to be essential for the final size of the nanocomposites and there was an optimal content that led to the synthesis of nanocomposites of 400–600 nm hydrodynamic size. The enhanced stability of the synthesized nanocomposites was assessed with LUMiSizer after synthesis. Nanocomposite stability over time and under variations of ionic strength and pH were assessed with dynamic light scattering. The rounded shapes of nanocomposites were confirmed by scanning electron microscopy. After loading with insulin, analysis by HPLC revealed complete drug release under physiologically simulated conditions.

Poly(4-styrene sulfonic acid)/bacterial cellulose membranes: Electrochemical performance in a single-chamber microbial fuel cell

The present work aims at exploiting a polyelectrolyte nanocomposite based on poly(4-styrene sulfonic acid) (PSSA) and bacterial cellulose (BC) as an eco-friendly proton-exchange membrane (PEM) for application in microbial fuel cells (MFCs). The PSSA/BC-based PEM was confirmed as a true nanocomposite by inelastic neutron scattering (INS) vibrational spectroscopy. Moreover, this PEM exhibited thermal stability up to 155 °C, Young's modulus of 11.7 ± 0.9 GPa, ion exchange capacity of 1.85 mmol g−1, and maximum protonic conductivity of 1.73 S m−1. The application of the PSSA/BC nanocomposite membrane in a single-chamber lab-scale MFC with a pure culture of Shewanella frigidimarina yielded a maximum power density of 2.42 mW m−2, open circuit voltage of 0.436 V, and internal resistance of 15.1 kΩ. These results are superior to those obtained with a commercial Nafion® membrane and, thus, confirm the potential of this bio-based PSSA/BC nanocomposite as a PEM for MFCs.

Is clay-polycation adsorbent future of the greener society? In silico modeling approach with comprehensive virtual screening

Presence of organic pollutants in the wastewater and aquatic environment is one of the serious concerns worldwide. Superior adsorption of organic pollutants on modified clays with organocations is well approved nowadays. Among hybrid materials, clay–polyelectrolyte nanocomposites (CPN) are one of the specifically designed materials for the efficient adsorption of diverse organic pollutants. Due to higher surface area of the clay mineral coupled with a polymer coating, they have an explicit affinity for the organic pollutants. In this background, we have developed statistically significant and mechanistically interpretable quantitative structure-property relationship (QSPR) model for adsorption coefficient of diverse organic pollutants to the protonated montmorillonite–poly-4-vinylpyridine-co-styrene (Mt–HPVPcoS), a hybrid CPN. Further, the model was employed to predict the logkd value of ∼0.9 million chemicals from five diverse databases spanning from existing and experimental pharmaceuticals, natural and synthetic chemicals and dyes with unknown logkd value for the mentioned CPN. The reliability of predicted data is checked with two layers confidence screening i.e. the applicability domain study followed by prediction quality check by ‘Prediction Reliability Indicator’. Thus, prediction of each compound can be used for data gap filling by environmental regulatory authorities as well as industries. Followed by, maximum common substructure-based (MCS) algorithm is employed for individual database to extract the important structural scaffold for higher logkd to the mentioned CPN.

Poly(bis[2-(methacryloyloxy)ethyl] phosphate)/Bacterial Cellulose Nanocomposites: Preparation, Characterization and Application as Polymer Electrolyte Membranes

Recent studies have demonstrated the potential of bacterial cellulose (BC) as a substrate for the design of bio-based ion exchange membranes with an excellent combination of conductive and mechanical properties for application in devices entailing functional ion conducting elements. In this context, the present study aims at fabricating polyelectrolyte nanocomposite membranes based on poly(bis[2-(methacryloyloxy)ethyl] phosphate) [P(bisMEP)] and BC via the in-situ free radical polymerization of bis[2-(methacryloyloxy)ethyl] phosphate (bisMEP) inside the BC three-dimensional network under eco-friendly reaction conditions. The resulting polyelectrolyte nanocomposites exhibit thermal stability up to 200 °C, good mechanical performance (Young’s modulus > 2 GPa), water-uptake ability (79–155%) and ion exchange capacity ([H+] = 1.1–3.0 mmol g−1). Furthermore, a maximum protonic conductivity of ca. 0.03 S cm−1 was observed for the membrane with P(bisMEP)/BC of 1:1 in weight, at 80 °C and 98% relative humidity. The use of a bifunctional monomer that obviates the need of using a cross-linker to retain the polyelectrolyte inside the BC network is the main contribution of this study, thus opening alternative routes for the development of bio-based polyelectrolyte membranes for application in e.g., fuel cells and other devices based on proton separators.

Polyelectrolyte Nanocomposite Membranes with Imidazole-Functionalized Multi-Walled Carbon Nanotubes for Use in Fuel Cell Applications

ABSTRACTThe preparation and characterization of a new type of nanocomposite polyelectrolyte membrane (PEM), based on Nafion® and imidazole modified multi-walled carbon nanotubes (MWCNT-Im), for direct methanol fuel cell (DMFC) applications is described. Related to the interactions between the protonated imidazole groups, grafted on the surface of multi-walled carbon nanotubes (MWCNT), and the negatively charged sulfonic acid groups of Nafion®, new electrostatic interactions can be formed in the interface of the Nafion® and MWCNT-Im which result in both lower methanol permeability and also higher proton conductivity. The physical characteristics of these manufactured nanocomposite membranes were investigated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), water uptake, methanol permeability and ion exchange capacity, as well as proton conductivity. The Nafion®/MWCNT-Im membranes showed higher proton conductivity, lower methanol permeability and, as a consequence, a higher selectivity parameter in comparison to neat Nafion® or Nafion® containing –OH functionalized multi-walled carbon nanotubes (MWCNT-OH) membranes. The obtained results indicated that the Nafion®/MWCNT-Im membranes could be utilized as efficient polyelectrolyte membranes for direct methanol fuel cell applications.

In Situ Growth and Characterization of Metal Oxide Nanoparticles within Polyelectrolyte Membranes.

This study describes a novel approach for the in situ synthesis of metal oxide-polyelectrolyte nanocomposites formed via impregnation of hydrated polyelectrolyte films with binary water/alcohol solutions of metal salts and consecutive reactions that convert metal cations into oxide nanoparticles embedded within the polymer matrix. The method is demonstrated drawing on the example of Nafion membranes and a variety of metal oxides with an emphasis placed on zinc oxide. The in situ formation of nanoparticles is controlled by changing the solvent composition and conditions of synthesis that for the first time allows one to tailor not only the size, but also the nanoparticle shape, giving a preference to growth of a particular crystal facet. The high-resolution TEM, SEM/EDX, UV-vis and XRD studies confirmed the homogeneous distribution of crystalline nanoparticles of circa 4 nm and their aggregates of 10-20 nm. The produced nanocomposite films are flexible, mechanically robust and have a potential to be employed in sensing, optoelectronics and catalysis.

In Situ Growth and Characterization of Metal Oxide Nanoparticles within Polyelectrolyte Membranes

AbstractThis study describes a novel approach for the in situ synthesis of metal oxide–polyelectrolyte nanocomposites formed via impregnation of hydrated polyelectrolyte films with binary water/alcohol solutions of metal salts and consecutive reactions that convert metal cations into oxide nanoparticles embedded within the polymer matrix. The method is demonstrated drawing on the example of Nafion membranes and a variety of metal oxides with an emphasis placed on zinc oxide. The in situ formation of nanoparticles is controlled by changing the solvent composition and conditions of synthesis that for the first time allows one to tailor not only the size, but also the nanoparticle shape, giving a preference to growth of a particular crystal facet. The high‐resolution TEM, SEM/EDX, UV‐vis and XRD studies confirmed the homogeneous distribution of crystalline nanoparticles of circa 4 nm and their aggregates of 10–20 nm. The produced nanocomposite films are flexible, mechanically robust and have a potential to be employed in sensing, optoelectronics and catalysis.

Preparation of hybrid fluorescent nanocomposites with enhanced fluorescence and their application

Abstract In this study, a kind of core–shell structured fluorescent nanocomposites was synthesized by self-assembly technique. To prepare these hybrid nanocomposites, multi-branched gold nanoparticles (MBG NPs) were employed as the core. And SiO 2 shells were coated on the MBG NPs to facilitate further modification. Polyelectrolyte (PE) multilayer composed of poly( l -lysine) (PLL) and poly(acrylic acid) (PAA) was further coated onto the MBG@SiO 2 nanocomposites to sever as the thickness controllable layer. Then positively charged porphyrin derivative 5,10,15,20-tetrakis(1-methyl-4-pyridinio) porphyrin tetra( p -toluenesulfonate) (Por 4+ ) was adsorbed on the prepared MBG@SiO 2 /PE nanocomposites as the fluorophore. The fluorescence intensity of Por 4+ was enhanced by 2.4-fold when three PLL/PAA bilayers were used as the PE multilayer. Meanwhile, the singlet oxygen generation property of Por 4+ has been accelerated at the presence of the prepared nanocomposites. And the nanocomposites show potential usage in efficient antibacterial experiment.

Pt nanoparticles on graphene – polyelectrolyte nanocomposite: Investigation of H2O2 and methanol electrocatalysis

Poly (diallyldimethylammonium chloride) (PDDA) functionalized graphene oxide (GO) decorated with Pt nanoparticles (PtNPs) was obtained and investigated. This hybrid nanocomposite material was morphologically characterized by several instrumental techniques like high-resolution transmission electron microscopy (HR-TEM), selected area electron diffraction (SAED) and X-ray diffraction (XRD). Good coverage of crystalline Pt nanoparticles was achieved, the average diameter being 2 nm, meanwhile in the absence of polyelectrolyte the average diameter increased up to 4 nm. The electrocatalytic properties of this hybrid nanocomposite against H2O2 and methanol were ascertained by cyclic voltammetry. A modified glassy carbon electrode (GC) was able to reduce H2O2 at positive potentials (starting from ∼150 mV vs. Ag/AgCl) meanwhile for methanol the ratio of the forward anodic peak current (If) to the reverse anodic peak current (Ib) was 1.42, indicating good tolerance of the catalyst towards the intermediate carbonaceous species accumulated on the electrode surface.

Hybrid silver nanoparticle/conjugated polyelectrolyte nanocomposites exhibiting controllable metal-enhanced fluorescence.

Metal-enhanced fluorescence of conjugated polyelectrolytes (CPs) is realized using a simple, green hybrid Ag nanocomposite film. Ag nanoparticles (Ag NPs) are pre-prepared by sodium citrate reduction and incorporated into agarose by mixing to form an Ag-containing agarose film (Ag@agarose). Through variation of the amount of Ag NPs in the Ag@agarose film as well as the thickness of the interlayer between CPs and the Ag@agarose film prepared of layer-by-layer assembly of chitosan and sodium alginate, a maximum 8.5-fold increase in the fluorescence of CPs is obtained. After introducing tyrosinase, this system also can be used to detect phenolic compounds with high sensitivity and good visualization under ultraviolet light.

Polyelectrolyte Nanocomposite Membranes, Based on Chitosan-phosphotungstic Acid Complex and Montmorillonite for Fuel Cells Applications

A polyelectrolyte complex (PEC) of chitosan and phosphotungstic acid (PWA) was prepared and characterized as a proton-conducting membrane for direct methanol fuel cell (DMFC) applications. Fourier transform infrared spectroscopy showed the presence of stable PWA in PEC. To reduce the methanol permeability, several amounts of montmorilonite (MMT) nanoclays (trade name: Cloisite Na) were introduced to the system. The X-ray diffraction patterns of nanocomposite membranes proved the nanoclay layers were exfoliated in the membranes at loading weights of MMT lower than 3 wt%. Proton conductivity and methanol permeability were measured. According to the selectivity parameter—ratio of proton conductivity to methanol permeability—PEC containing 2 wt% MMT (PEC/2 wt% MMT) was identified as the optimum composition. Finally, DMFC performance tests were investigated at 70°C and 5 M methanol feed and the optimum membrane showed higher maximum power density in comparison with Nafion 117. The results indicated the optimum nanocomposite membrane is a promising polyelectrolyte membrane (PEM) for DMFC applications.

Enhanced Dewatering of Polyelectrolyte Nanocomposites by Hydrophobic Polyelectrolytes

We demonstrate that increasing the hydrophobic environment around the charge center of a polyelectrolyte (PE) not only decreases the water content of an adsorbed PE layer but can even dewater up to ~50% of an initially hydrated substrate. The results of this work are expected to yield new stratagies to dewater PE systems and have potential applications in mineral recovery, paper manufacturing, and biomedical materials. Adsorption of a series of cationically derivatized dextran polyelectrolytes onto sulfated nanocrystalline cellulose (SNC) has been studied using quartz crystal microbalance with dissipation monitoring (QCM-D) and surface plasmon resonance (SPR). Synthesized samples of (N,N-dimethylamino)ethyldextran (DMAE-Dex), (N,N-diethylamino)ethyldextran (DEAE-Dex), and (N,N-diisopropylamino)ethyldextran (DIAE-Dex) had degrees of substitution (DS) ranging from 0.05 to 0.82. DMAE-Dex, DEAE-Dex, and DIAE-Dex all showed decreasing adsorption onto SNC and decreasing water content of the adsorbed film with increasing DS. Additionally, DEAE-Dex and DIAE-Dex films adsorbed onto SNC contained less water than DMAE-Dex films with the same DS. Interestingly, QCM-D results for high DS DIAE-Dex adsorbed onto SNC revealed mass loss, whereas SPR results clearly showed DIAE-Dex adsorbed. These observations were consistent with dehydration of the SNC substrate. This study indicates that the water content of the substrate could be tailored by controlling the DS and hydrophobic character of the adsorbed polyelectrolytes.

Synthesis and High Performance of Magnetofluorescent Polyelectrolyte Nanocomposites as MR/Near-Infrared Multimodal Cellular Imaging Nanoprobes

Here, we describe an easy but robust chemical strategy to synthesize high-performance magnetic resonance (MR)/near-infrared (NIR) multimodal imaging nanoprobes. Poly(γ-glutamic acid) was used for the convenient phase transfer of MnFe(2)O(4) nanoparticles dispersed in organic solvents into aqueous solutions and facilitated further ionic gelation with poly(l-lysine). During the gelation process, MnFe(2)O(4) nanoparticulate satellites were encapsulated in the ionic nanocomplex, which induced synergistic magnetism and resulted in huge T(2) relaxivity (r(2)). The positively charged outer surfaces were assembled with other negatively charged NIR emitting fluorescent nanocrystals and enabled the highly efficient delivery of the magnetofluorescent polyelectrolyte nanocomposites (MagFL-PEN) into cancer cells. The enhancement of negative contrast of MagFL-PEN at 2 μg/mL concentration was similar to that of Resovist at 20 μg/mL concentration. The NIR fluorescence microscopy images of the MagFL-PEN-labeled cells even at 12.5 pM were able to be clearly observed. The labeling efficiency of MagFL-PEN was approximately 65-fold higher compared to that of the commercialized fluorescent nanocrystals, only after 3 h incubation period, even at the test concentration (100 pM). Due to the high-performance capabilities both in materials properties and cell labeling efficiency, the MagFL-PEN is expected to be used as a highly efficient MR/NIR dual-modality imaging nanoprobe in the detection of cancer cells and monitoring of therapeutic cells in vivo.

Elastic Moduli of Asymmetric Ultrathin Free-Standing Polyelectrolyte Nanocomposites

We have developed a novel technique for the elucidation of the mechanical behavior of ultrathin free-standing materials and demonstrate results using polyelectrolyte nanocomposites with thicknesses between 1 and 10 nm. In short, a charged molecular template is deposited on a pendant drop and compressed to present a defined surface charge density to the subphase of the drop. The subphase is then cycled alternately between polyelectrolyte solutions to achieve electrostatic layer-by-layer assembly of an ultrathin nanocomposite at the drop surface. The stress response of the membrane-laden drop to dilation of its surface as measured by axisymmetric drop shape analysis is compared with a two-dimensional continuum model. The impact of surface charge density of the template and the film thickness on the two-dimensional elastic modulus, Eg, of the nanocomposite were assessed, and mechanical behavior consistent with that of an elastomeric solid is demonstrated.