Negative Polyelectrolytes Research Articles

Antifouling Coatings from Glassy Polyelectrolyte Complex Films.

Coatings that prevent or decrease fouling are sought for many applications, including those that inhibit the attachment of organisms in aquatic environments. To date, antifouling coatings have mostly followed design criteria assembled over decades: surfaces should be well/strongly hydrated, possess low net charge, and maintain a hydrophilic character when exposed to the location of use. Thus, polymers based on ethylene glycol or zwitterionic repeat units have been shown to be highly effective. Unfortunately, hydrated materials can be quite soft, limiting their use in some environments. In a major paradigm shift, this work describes glassy antifouling films made from certain complexes of positive and negative polyelectrolytes. The dense network of electrostatic interactions yields tough materials below the glass transition temperature, Tg, in normal use, while the highly ionic character of these polyelectrolyte complexes ensures strong hydration. The proximity of equal numbers of opposite charges within these complexes mimics zwitterionic structures. Films, assembled layer-by-layer from aqueous solutions, contained sulfonated poly(ether ether ketone), SPEEK, a rigid polyelectrolyte that binds strongly to a selection of quaternary ammonium polycations. Layer-by-layer buildup of SPEEK and polycations was linear, indicating strong complexes between polyelectrolytes. Calorimetry also showed that complex formation was exothermic. Surfaces coated with these films in the 100 nm thickness range completely resisted adhesion of the common flagellate green algae, Chlamydomonas reinhardtii, which were removed from surfaces at a minimum applied flow rate of 0.8 cm s-1. The total surface charge density of adsorbed cations, determined with a sensitive radioisotopic label, was very low, around 10% of a monolayer, which minimized adsorption driven by counterion release from the surface. The viscoelastic properties of the complexes, which were stable even in concentrated salt solutions, were explored using rheology of bulk samples. When fully hydrated, their Tg values were observed to be above 75 °C.

Alternating electric field-based ionic control and layer-by-layer assembly of anion exchange membranes for enhancing target anion selectivity

Separation and recovery of target anions from wastewater is a sustainable method for chemical production industry. In this study, the novel anion exchange membranes with high antifouling and target ion selectivity performance were designed by the layer-by-layer (LbL) assembly of dopamine, positive and negative polyelectrolytes under the alternating current electric field and ionic control (AC[ion]) process. The resulting membranes were fabricated with different LbL assembled multilayers to evaluate the target ion selectivity. Besides, the different LbL assembled methods, including the electrostatic deposition self-assembly (EDS), AC[Cl−] assembly and AC[NO3−] assembly methods were carried out to evaluate the ion effect in membrane assembly process on final target ion permeation rate, respectively. With the initial concentration of 50 mM of NaCl, NaNO3 and Na2SO4 in mixed solution and the constant current density of 5.00 mA cm−2 of electrodialysis, the permselectivity of resulting membrane could be enhanced by the increased multilayers. Besides, the ion control in the alternating current electric field assembly process could enhance the relevant target ion permeation rate. The increased values of membrane surface electrical resistance fouled by organic pollutants were used to evaluate the antifouling property of membranes in electrodialysis, and the resulting membranes showed a high antifouling performance. This work provided a promising membrane separation technology in target anion recovery from wastewater for sustainable development.

Control and Preparation of Quaternized Chitosan and Carboxymethyl Chitosan Nanoscale Polyelectrolyte Complexes Based on Reactive Flash Nanoprecipitation.

Nanoscale polyelectrolyte complex materials have been extensively investigated for their promising application in protocell, drug carriers, imaging, and catalysis. However, the conventional preparation approach involving positive and negative polyelectrolytes leads to large size, wide size distribution, instability, and aggregation due to the nonhomogeneous mixing process. Herein, we employ reactive flash nanoprecipitation (RFNP) to control the mixing and preparation of the nanoscale polyelectrolyte complex. With RFNP, homogeneous mixing complexation between oppositely charged chitosan derivatives could be achieved, resulting in stable nanoscale complexes (NCs) with controllable size and narrow size distribution. The smallest size of NCs is found at specific pH due to the maximum attraction of positive and negative molecules of chitosan. The size can be modulated by altering the volumetric flow rates of inlet streams, concentration, and charge molar ratio of two oppositely charged chitosan derivatives. The charge molar ratio is also tuned to create NCs with positive and negative shells. There is no significant variation in the size of NCs produced at different intervals of time. This method allows continuous and tunable NC production and could have the potential for fast, practical translation.

Polyelectrolyte-Assisted Dispersions of Reduced Graphite Oxide Nanoplates in Water and Their Gas-Barrier Application.

Dispersion of graphene and related materials in water is needed to enable sustainable processing of these 2D materials. In this work, we demonstrate the capability of branched polyethylenimine (BPEI) and polyacrylic acid (PAA) to stabilize reduced graphite oxide (rGO) dispersions in water. Atomic force microscopy colloidal probe measurements were carried out to investigate the interaction mechanisms between rGO and the polyelectrolytes (PEs). Our results show that for positive PEs, the interaction appears electrostatic, originating from the weak negative charge of graphene in water. For negative PEs, however, van der Waals forces may result in the formation of a PE shell on rGO. The PE-stabilized rGO dispersions were then used for the preparation of coatings to enhance gas barrier properties of polyethylene terephthalate films using the layer-by-layer self-assembly. Ten bilayers of rGOBPEI/rGOPAA resulted in coatings with excellent barrier properties as demonstrated by oxygen transmission rates below detection limits [<0.005 cm3/(m2 day atm)]. The observed excellent performance is ascribed to both the high density of the deposited coating and its efficient stratification. These results can enable the design of highly efficient gas barrier solutions for demanding applications, including oxygen-sensitive pharmaceutical products or flexible electronic devices.

MobiDB-lite 3.0: fast consensus annotation of intrinsic disorder flavors in proteins.

The earlier version of MobiDB-lite is currently used in large-scale proteome annotation platforms to detect intrinsic disorder. However, new theoretical models allow for the classification of intrinsically disordered regions into subtypes from sequence features associated with specific polymeric properties or compositional bias. MobiDB-lite 3.0 maintains its previous speed and performance but also provides a finer classification of disorder by identifying regions with characteristics of polyolyampholytes, positive or negative polyelectrolytes, low-complexity regions or enriched in cysteine, proline or glycine or polar residues. Subregions are abundantly detected in IDRs of the human proteome. The new version of MobiDB-lite represents a new step for the proteome level analysis of protein disorder. Both the MobiDB-lite 3.0 source code and a docker container are available from the GitHub repository: https://github.com/BioComputingUP/MobiDB-lite.

Coating Effect on the 1H-NMR Relaxation Properties of Iron Oxide Magnetic Nanoparticles.

We present a 1H Nuclear Magnetic Resonance (NMR) relaxometry experimental investigation of two series of magnetic nanoparticles, constituted of a maghemite core with a mean diameter dTEM = 17 ± 2.5 nm and 8 ± 0.4 nm, respectively, and coated with four different negative polyelectrolytes. A full structural, morpho-dimensional and magnetic characterization was performed by means of Transmission Electron Microscopy, Atomic Force Microscopy and DC magnetometry. The magnetization curves showed that the investigated nanoparticles displayed a different approach to the saturation depending on the coatings, the less steep ones being those of the two samples coated with P(MAA-stat-MAPEG), suggesting the possibility of slightly different local magnetic disorders induced by the presence of the various polyelectrolytes on the particles’ surface. For each series, 1H NMR relaxivities were found to depend very slightly on the surface coating. We observed a higher transverse nuclear relaxivity, r2, at all investigated frequencies (10 kHz ≤ νL ≤ 60 MHz) for the larger diameter series, and a very different frequency behavior for the longitudinal nuclear relaxivity, r1, between the two series. In particular, the first one (dTEM = 17 nm) displayed an anomalous increase of r1 toward the lowest frequencies, possibly due to high magnetic anisotropy together with spin disorder effects. The other series (dTEM = 8 nm) displayed a r1 vs. νL behavior that can be described by the Roch’s heuristic model. The fitting procedure provided the distance of the minimum approach and the value of the Néel reversal time (τ ≈ 3.5 ÷ 3.9·10−9 s) at room temperature, confirming the superparamagnetic nature of these compounds.

A fully bio-based coating made from alginate, chitosan and hydroxyapatite for protecting flexible polyurethane foam from fire

The present study reports the successful synthesis of the flame-retardant and smoke-suppressant flexible polyurethane foam (FPUF) through a fully bio-based coating. Hydroxyapatite (HAP) is added to the solutions containing sodium alginate (SA) and chitosan (CH), respectively, to create negative and positive polyelectrolytes for Layer-by-Layer (LbL) assembly. The influence of the solution concentrations and bilayers numbers deposited on the flame-retardant and mechanical properties of FPUF samples is investigated systematically. Benefitting from the presence of such a fully bio-based coating, the resultant FPUF affords excellent smoke-suppressant and flame-retardant features. In particular, the FPUF coated by 9 bilayers of HAP-SA/HAP-CH exhibits significantly declined peak heat release rate, total release rate and smoke production release by 77.7 %, 56.5 % and 53.8 %, respectively. The compression test verifies the coated FPUFs exhibit lower recovery properties compared with the uncoated one. These results demonstrate that a green and cost-effective strategy is provided for producing flame-retardant, anti-dripping and smoke-suppressant FPUFs.

Ion-Pairing Strength in Polyelectrolyte Complexes

Polyelectrolyte complexes, PECs, are spontaneously formed blends of polyelectrolytes bearing positive, Pol+, and negative, Pol–, repeat units. Many interesting PEC morphologies have been observed, ranging from dense precipitates to liquidlike coacervates to quasi-stable nanoparticles, depending on the identity of the polymers and the preparation conditions. While the number of polyelectrolytes available to synthesize these materials is large and increasing, the corresponding number of Pol+/Pol– combinations is vast. This work quantitatively compares the binding strengths between a selection of positive and negative polyelectrolytes by evaluating the extent to which ion pairs between them are broken by a common salt, KBr. Comparison of association constants or Gibbs free energies between different classes of ionic functionality reveals that more “hydrophilic” PECs are more weakly associated, small primary amines bind strongly, carboxylates bind weakly, and aromatic sulfonates interact more strongly than al...

Dendrite Suppression by Shock Electrodeposition in Charged Porous Media.

It is shown that surface conduction can stabilize electrodeposition in random, charged porous media at high rates, above the diffusion-limited current. After linear sweep voltammetry and impedance spectroscopy, copper electrodeposits are visualized by scanning electron microscopy and energy dispersive spectroscopy in two different porous separators (cellulose nitrate, polyethylene), whose surfaces are modified by layer-by-layer deposition of positive or negative charged polyelectrolytes. Above the limiting current, surface conduction inhibits growth in the positive separators and produces irregular dendrites, while it enhances growth and suppresses dendrites behind a deionization shock in the negative separators, also leading to improved cycle life. The discovery of stable uniform growth in the random media differs from the non-uniform growth observed in parallel nanopores and cannot be explained by classic quasi-steady “leaky membrane” models, which always predict instability and dendritic growth. Instead, the experimental results suggest that transient electro-diffusion in random porous media imparts the stability of a deionization shock to the growing metal interface behind it. Shock electrodeposition could be exploited to enhance the cycle life and recharging rate of metal batteries or to accelerate the fabrication of metal matrix composite coatings.

Magnetorheology of core–shell typed dual-coated carbonyl iron particle fabricated by a sol–gel and self-assembly process

Micron-sized soft-magnetic carbonyl iron (CI) particles, which are the most widely applied magnetic particles in magnetorheological (MR) fluids, were evaluated as a candidate for modification by coating to reduce their density and provide rich surface properties. Both silica and multi-walled carbon nanotubes (MWNTs) dual-coated soft-magnetic CI particles were fabricated and applied as magneto-responsive solid particles in an MR fluid. The silane-grafted CI microspheres were coated with the first layer of silica using a sol–gel method, and the second layer of MWNTs was then wrapped using a layer-by-layer process in both positive and negative polyelectrolytes. The rheological properties from the dynamic and steady shear tests of the MR fluid when dispersed in silicone oil were examined using a rotational rheometer under an applied magnetic field. The Schwarzl equation was also used to determine relaxation modulus of the MR fluid, based on the dynamic moduli measured from a frequency sweep method.

Layer-by-Layer Thin Films of Alginate/Chitosan and Hyaluronic Acid/Chitosan with Tunable Thickness and Surface Roughness

Layer-by-layer (LbL) is a bottom-up technique used for construction of films with self-assembly and self-organizing properties. In most cases, the fundamental driving force for the formation of these films is originated from the electrostatic interaction between oppositely charged species. The charged segments of polyelectrolytes behave as small building units and their orientation and position can be designed to target structures of great complexity. Furthermore, the technique enables the use of various materials, including natural polymers. In this work, we chose the cationic biopolymer chitosan (CHI) and the negative polyelectrolytes sodium alginate (ALG) and hyaluronic acid (HA). The aim of this study was to evaluate the effect of ionic strength (0 versus 200 mM) and pH (3 versus 5) on ALG/CHI and HA/CHI nanostructured multilayered thin films properties. From profilometry and atomic force microscopy (AFM) analyses, changes in thickness and roughness of the coatings were monitored. The presence of salt in polyelectrolyte solutions induced the polymer chains to adopt conformations with more loops and tails and this arrangement in solution was transmitted to films, resulting in rougher surfaces. Furthermore, the film thickness can be precisely controlled by adjusting the pH of the polyelectrolyte solution. The variation of these parameters shows that it is possible to molecularly control chemical and structural properties of nanostructured coatings, thus opening up new possibilities of application (e.g. cell adhesion).

Carbon nanotube-coated silicated soft magnetic carbonyl iron microspheres and their magnetorheology

Core-shell structured magnetic microspheres were fabricated by coating the surface of silicated soft magnetic carbonyl iron particles with multi-walled carbon nanotubes using a facile layer-by-layer method involving an alternative sequential adsorption of positive and negative polyelectrolytes. The morphology of the fabricated particles was observed by scanning electron microscopy. The magnetorheological (MR) behavior affected by the non-magnetic coatings was examined using a rotational rheometer under a controlled magnetic field. The flow curves of typical MR characteristics with improved shear stresses were observed under a range of magnetic field strengths.

Correlating the Compliance and Permeability of Photo-Cross-Linked Polyelectrolyte Multilayers

Photo-cross-linkable polyelectrolyte multilayers were made from poly(allylamine) (PAH) and poly(acrylic acid) (PAA) modified with a photosensitive benzophenone. Nanoindentation, using atomic force microscopy (AFM) of these and unmodified PAH/PAA multilayers, was used to assess their mechanical properties in situ under an aqueous buffer. Under the conditions employed (and a 20 nm radius AFM tip), reliable nanoindentations that appeared to be decoupled from the properties of the silicon substrate were obtained for films greater than 150 nm in thickness. A strong difference in the apparent modulus was observed for films terminated with positive as compared to negative polyelectrolytes. Films terminated with PAA were more glassy, suggesting better charge matching of polyelectrolytes. Multilayers irradiated for up to 100 min showed a smooth, controlled increase in the modulus with little change in the water contact angle. The permeability to iodide ion, measured electrochemically, also decreased in a controlled fashion.

Multilayer films of cationic graphene-polyelectrolytes and anionic graphene-polyelectrolytes fabricated using layer-by-layer self-assembly

Extremely thin sheets of carbon atoms called graphene have been predicted to possess excellent thermal properties, electrical conductivity, and mechanical stiffness. To harness such properties in composite materials for multifunctional applications, one would require the incorporation of graphene. In this study, new thin film composites were created using layer-by-layer (LBL) assembly of polymer-coated graphitic nanoplatelets. The positive and negative polyelectrolytes used to cover graphene sheets were poly allylamine hydrochloride (PAH) and poly sodium 4-styrenesulfonate (PSS). The synthesized poly allylamine hydrochloride-graphene (PAH-G) and poly sodium 4-styrenesulfonate-gaphene (PSS-G) were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and thermo gravimetric analysis (TGA). The multilayer films created by spontaneous sequential adsorption of PAH-G and PSS-G were characterized by ultra violet spectroscopy (UV–vis), scanning electron microscopy (SEM), and AFM. The electrical conductivity of the graphene/polyelectrolyte multilayer film composites measured by the four-point probe method was 0.2 S cm −1, which was sufficient for the construction of advanced electro-optical devices and sensors.

Solubility of neutral and charged polymers in ionic liquids studied by laser light scattering

The solubility and chain conformation of different types of homopolymers in low viscosity ionic liquids (ILs), 1-allyl-3-methylimidazolium chloride ([AMIM][Cl]) at 50 °C and 1-butyl-3-methylimidazolium formate ([BMIM][COOH]) at 25 °C, were studied by laser light scattering (LLS). For neutral polymers, such as polyvinyl alcohol and polysulfonamide, aggregation occurred in all the cases except for polyvinyl alcohol in [BMIM][COOH]. For negative polyelectrolytes, such as DNA and polystyrene sulfonate, single chain conformation was observed. However, the hydrodynamic radius of both polymers was much smaller than that in good solvents, suggesting that the chains were condensed. Cellulose was soluble in [AMIM][Cl], and non-diffusive mode was observed by dynamic light scattering. Zeta potential analysis indicated that cellulose exhibited the feature of polyelectrolyte. The solubility of homopolymers could be qualitatively explained by treating polymer/IL as a ternary system: polymer, cation, and anion. It was the mutual interactions determined the solubility and conformation of polymers in ILs.

Effect of plasma-treated polymer substrates on fabricating surface microsystems through LbL coating

The surface free energy of three polymeric substrates, PMMA (poly(methyl methacrylate)), PS (polystyrene) and PC (polycarbonate), subjected to a RF O2 plasma treatment and washing with water was studied with the aim of fabricating surface micro-systems using a LbL technique. More uniform hysteresis of the deionized(DI) water contact angle after the plasma treatment followed by washing with water was observed on the PS surface compared to that on the PMMA and PC surfaces. XPS showed that washing with water may alter the plasma generated functionality, which readily forms oxygen containing groups, such as C=O and O-C=O. The surface free energy measured by the acid-base method showed that the Lewis base components on PS were less affected than those on PMMA and PC, due to the weak solvent effect of the former. During the LbL coating of the polyelectrolyte, the solvent effect was less likely to occur on PS, which exhibited better electrostatic bonding of the positive and negative polyelectrolytes (PEL). The fluorescence intensity was similar to the above findings, which may help determine the best substrate for surface micro-patterning using the LbL technique.

Hydration Contributions to Association in Polyelectrolyte Multilayers and Complexes: Visualizing Hydrophobicity

Thin films of polyelectrolyte complex were assembled using the multilayering method with direct, in situ observation of all multilayer components using attenuated total internal reflectance FTIR (ATR-FTIR). Buildup and ion doping of two representative combinations of positive and negative polyelectrolytes are controlled by salt type. The internal hydration of multilayers, measured precisely by ATR-FTIR, depends on the chemical identities of the polymers and the salt ions. The efficiency of doping inversely tracks the degree of hydration: less hydrated ("hydrophobic") ions are more efficient dopants, and less hydrated polyelectrolye complexes are harder to dope. Given that polyelectrolyte complexation is essentially entropy-driven, driving forces for doping, or association (the inverse of doping), are rationalized by counting all species in the condensed polyelectrolyte phase, including water molecules. For any combination of uni-univalent salt ions and polyelectrolyte, the strength of polyelectrolyte association is described by a single universal parameter. The magnitudes of the interactions per repeat unit are not high--a few kT--and are proportional to the number of water molecules released from the polymers when they form ion pairs. Hydration within multilayers due to residual salt is extensive but may be removed by an external osmotic stressing agent.

Key considerations in the determination of polyelectrolyte concentration by the colloidal titration method

Medium or high charge density cationic polyelectrolytes are frequently used for water treatment. In the papermaking wet-end they are used as retention agents or as flocculating aids. Negative polyelectrolytes that enter the papermaking system increase the demand for cationic polyelectrolytes. Polyelectrolyte concentration can be determined by the colloidal titration method, using either of two options for detecting the endpoint: i) visual observation or spectrophotometric determination of the colour change of an indicator, or ii) streaming current measurement. This work discusses the best conditions for the application of the titration using spectrophotometric measurement for the end point detection. Poly-diallyldimethylammonium chloride was used as the cationic polyelectrolyte, potassium polyvinyl sulphate as the negative polyelectrolyte, and o-toluidine blue as the positive indicator dye. The polyelectrolyte concentration range, interference from the metal ions affecting the indicator color change, the optimal indicator concentration to avoid precipitation problems, and the effect of adding a surfactant to the indicator solution were also considered. Titration curves were analyzed and optimized. Under these conditions the technique provided results with acceptable precision.

Catch and Release of DNA in Coacervate‐Dispersed Gels

AbstractSummary: We have synthesized novel coacervate‐droplet gels, which were applied to controlling the transportation of DNA in electrophoresis. Coacervate droplets are colloidal particles and they are usually composed of positive and negative polyelectrolytes. However, the polyzwitterion (polyampholyte) PDMAPS can form coacervate droplets in water by itself, since PDMAPS has both positive and negative charges in each side group of main chain. Coacervate droplets have a unique nature and can catch charged macromolecules such as DNA. In order to utilize the nature of the PDMAPS coacervate droplets for the catch and release of DNA, we stabilized PDMAPS droplets in gels. The droplets catch the DNA in electrophoresis and the release of DNA can be controlled by temperature and salt addition.Electrophoresis of DNA, using coacervate‐dispersed PAAm gels, prepared at various PDMAPS concentrations. The circles indicate the PAAm gels embedded in agarose gels.magnified imageElectrophoresis of DNA, using coacervate‐dispersed PAAm gels, prepared at various PDMAPS concentrations. The circles indicate the PAAm gels embedded in agarose gels.

Atomic Layer Deposition to Fine-Tune the Surface Properties and Diameters of Fabricated Nanopores.

Atomic layer deposition of alumina enhanced the molecule sensing characteristics of fabricated nanopores by fine-tuning their surface properties, reducing 1/f noise, neutralizing surface charge to favor capture of DNA and other negative polyelectrolytes, and controlling the diameter and aspect ratio of the pores with near single Ångstrom precision. The control over the chemical and physical nature of the pore surface provided by atomic layer deposition produced a higher yield of functional nanopore detectors.