Charged Polymer Research Articles

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 30 h 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.Graphical abstract

Thermodynamic driving forces in contact electrification between polymeric materials

Contact electrification, or contact charging, refers to the process of static charge accumulation after rubbing, or even simple touching, of two materials. Despite its relevance in static electricity, various natural phenomena, and numerous technologies, contact charging remains poorly understood. For insulating materials, even the species of charge carrier may be unknown, and the direction of charge-transfer lacks firm molecular-level explanation. Here, we use all-atom molecular dynamics simulations to investigate whether thermodynamics can explain contact charging between insulating polymers. Based on prior work suggesting that water-ions, such as hydronium and hydroxide ions, are potential charge carriers, we predict preferred directions of charge-transfer between polymer surfaces according to the free energy of water-ions within water droplets on such surfaces. Broad agreement between our predictions and experimental triboelectric series indicate that thermodynamically driven ion-transfer likely influences contact charging of polymers. Furthermore, simulation analyses reveal how specific interactions of water and water-ions proximate to the polymer-water interface explain observed trends. This study establishes relevance of thermodynamic driving forces in contact charging of insulators with new evidence informed by molecular-level interactions. These insights have direct implications for future mechanistic studies and applications of contact charging involving polymeric materials.

Impact of specific ion effects and electrostatic interactions on a polyelectrolyte-polyampholyte complex

A complex overlay of interactions governs the conformations of polymers in solution. Among them, electrostatic interactions are the dominating factor for governing the dynamics of charged macromolecules. Salt ions further impact the conformations by inducing screening of the electrostatic interactions of the polymers. Polyelectrolytes and polyampholytes are two majorly used charged polymers for engineering hydrogels. These polymers form a complex when added together in a solution. This article emphasises the effect of salts on the polyelectrolyte-polyampholyte complex. The interactions have been analysed through the viscosity and diffusivity measurements. The in-depth analysis of the specific ion effect along with the viscous effect induced by the polymer has been carried out. It was concluded that the viscous effect tends to reverse the impact of salts on the electrostatic-dominated conformations of the polymers. The ‘Shear Dependent Generalised Intrinsic Viscosity’ (SDGIV) have been used to gain insights into the interactions between the polymers. Finally, the scaling of the viscosity with respect to the polymer concentration and the impact of the salts on the same has also been studied. It is concluded that the viscous effect of the polymers should also be considered for analysing the specific ion effects of the salts on the charged polymers.Graphical

Mathematical model of discharge and charge in rechargeable polymer based lithium-ion battery

Shepherd’s model is considered as an improved and simple to-apply battery dynamic model. The experimental nominal parameters of five different capacities of Lithium-ion Polymer battery samples are established from the manufacturer’s datasheets. The discharge and charge dynamics of the battery sample with the highest capacity, 3100 mAh are examined and validated. The clarity to derive the dynamic model parameters from the battery datasheet is a fascinating attribute of this model. The experimental database is utilized to study its dynamic feature and subsequently the dynamic battery model, which describes the relationship between the state of charge, the open circuit voltage and ambient temperature. The model is implemented and simulated by using MATLAB/Simulink tools. The current charge-discharge equations describe the optimized electrochemical activities with sustainable long cycle duration. The temperature model brings under control the aging effect, which plays down on the energy capacity of the battery. A steady load of 5 A is linked to the battery and used in a detail simulation of a direct current machine in determination of load effect. The compatibility of these equations and simulations implies that Shepherd’s model is promising to provide guidelines for the analysis of discharge and charge in rechargeable polymer based lithium-ion batteries. The results show that the model can precisely illustrate the dynamic behavior of the batteries.

Rapid alkalinization factor 22 has a structural and signalling role in root hair cell wall assembly.

Pressurized cells with strong walls make up the hydrostatic skeleton of plants. Assembly and expansion of such stressed walls depend on a family of secreted RAPID ALKALINIZATION FACTOR (RALF) peptides, which bind both a membrane receptor complex and wall-localized LEUCINE-RICH REPEAT EXTENSIN (LRXs) in a mutually exclusive way. Here we show that, in root hairs, the RALF22 peptide has a dual structural and signalling role in cell expansion. Together with LRX1, it directs the compaction of charged pectin polymers at the root hair tip into periodic circumferential rings. Free RALF22 induces the formation of a complex with LORELEI-LIKE-GPI-ANCHORED PROTEIN 1 and FERONIA, triggering adaptive cellular responses. These findings show how a peptide simultaneously functions as a structural component organizing cell wall architecture and as a feedback signalling molecule that regulates this process depending on its interaction partners. This mechanism may also underlie wall assembly and expansion in other plant cell types.

Separation of Polymeric Charge Enables Efficient Bipolar Membrane Operation

Separation of Polymeric Charge Enables Efficient Bipolar Membrane Operation

Optical pH Sensor Based on a Long-Period Fiber Grating Coated with a Polymeric Layer-by-Layer Electrostatic Self-Assembled Nanofilm.

An optical fiber pH sensor based on a long-period fiber grating (LPFG) is reported. Two oppositely charged polymers, polyethylenimine (PEI) and polyacrylic acid (PAA), were alternately deposited on the sensing structure through a layer-by-layer (LbL) electrostatic self-assembly technique. Since the polymers are pH sensitive, their refractive index (RI) varies when the pH of the solution changes due to swelling/deswelling phenomena. The fabricated multilayer coating retained a similar property, enabling its use in pH-sensing applications. The pH of the PAA dipping solution was tuned so that a coated LPFG achieved a pH sensitivity of (6.3 ± 0.2) nm/pH in the 5.92-9.23 pH range. Only two bilayers of PEI/PAA were used as an overlay, which reduces the fabrication time and increases the reproducibility of the sensor, and its reversibility and repeatability were demonstrated by tracking the resonance band position throughout multiple cycles between different pH solutions. With simulation work and experimental results from a low-finesse Fabry-Perot (FP) cavity on a fiber tip, the coating properties were estimated. When saturated at low pH, it has a thickness of 200 nm and 1.53 ± 0.01 RI, expanding up to 310 nm with a 1.35 ± 0.01 RI at higher pH values, mostly due to the structural changes in the PAA.

Selective detection of nanomaterials: Gold nanorod imprinted matrices

Anisotropic nanostructures such as nanorods can be found in an increasing number of applications such as catalysis and imaging. Although their synthesis is well developed, their selective detection and separation are still in their infancy. Here, we demonstrate for the first time the selective recognition of gold nanorods (GNRs) by the nanoparticle-imprinted matrix (NAIM) approach. Specifically, GNRs stabilized by citrate (GNRs-cit) were adsorbed on an electrode surface modified with a positively charged polymer. The adsorption was followed by the electrochemical deposition of an aryldiazonium-based matrix around the GNRs-cit. Nanocavities having the shape of the imprinted GNRs were formed upon the removal of the nanoobject by electrochemical dissolution. We find that these nanocavities showed the ability to reuptake selectively GNRs similar to those initially imprinted. Furthermore, our findings clearly show that the recognition of the GNRs, namely, their reuptake by the nanocavities, depends on both the physical, i.e., structural fitness, and the chemical interactions between the imprinted GNRs and the matrix. For example, whereas a matrix bearing carboxylic acid functionalities repelled the GNRs stabilized by citric acid, a matrix formed by the electropolymerization of 4-acetylbenzenediazonium (ABD) exhibited good reuptake. A reuptake percentage, which is the ratio between the number of GNRs uptaken by the nanocavities divided by the number of the originally imprinted GNRs, of ca. 50% was obtained.

Manufacturing nearly monodispersed complex coacervate microcapsules by membrane emulsification and spray drying

Complex coacervation is a phase separation process in which two oppositely charged polymers or macromolecules in a solution come together at the liquid-liquid interface to form a dense coacervate shell. The process can be employed to encapsulate oil droplets, creating stable microcapsules that protect and control the release of oil while achieving a high encapsulation efficiency of active ingredients. In this work dry coacervate microcapsules of different size and shell thickness were manufactured combining a continuous single pass cross-flow membrane emulsification system and spray drying to obtain a dry powder. A single-pass crossflow membrane emulsification system with a single cylindrical 10 × 100 mm membrane module with 10 μm pore produced emulsion droplets between 71 μm and 114 μm with a dispersed phase (oil content) in the final emulsion between 3.3 and 6.2 vol/vol% and a total emulsion output mass rate between 25.68 kg h−1 – 49.68 kg h−1. Emulsions manufactured by membrane emulsification were nearly monodispersed with the highest span not exceeding 0.68. Addition of maltodextrin to the emulsion prior to spray drying increased the viscosity and prevented the capsules breakage. Microcapsules up to a mean droplet diameter of 113.19 ± 0.81 μm preserved the shell and had a yield up to 78.43 ± 0.97 wt%, a surface oil as low as 9.35 ± 0.88 wt% and an encapsulation efficiency of 71.09 ± 0.87 wt%.

Carrageenan derived polyelectrolyte complexes material: An effective bifunctional for electrochemical sensing of sulfamethazine and antibacterial activity

Biopolymer-derived polyelectrolyte complexes (PECs) are a class of materials that have emerged as promising candidates for developing advanced electrochemical sensors due to their tunable properties, biocompatibility, cost-effective production, and high surface area. PECs are formed by combining positively and negatively charged polymers, resulting in a network with intriguing properties that can be tailored for specific sensing applications. The resultant PECs-based nanocomposites were used to modify the glassy carbon electrode (GCE) to detect the sulfamethazine (SFZ) antibiotic drug. In addition, electrochemical studies using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and differential pulse voltammetry (DPV) are used to evaluate the SFZ detection ability. Similarly, various microscopic and spectroscopic studies investigated the nano composite's structural features and morphological behavior. The κ-CGN/P(Am-co-DMDAAc)-GO modified GCE demonstrated excellent detection ability of SFZ with the nano molar range and without interference with similar structural components. Furthermore, the newly fabricated electrode κ-CGN/P(Am-co-DMDAAc)-GO was derived from naturally available materials, water-soluble, low cost, biocompatible, exhibits good conductivity, and excellent catalytic properties. Finally, κ-CGN/P(Am-co-DMDAAc)-GO- modified GCE has versatile, practical applications for detecting SFZ in real-time samples and determining the efficacy of an antibacterial activity.

In Vitro Detection of Lactate and Uric Acid Based on Adaptive Graphene Oxide Membranes

In vitro detection of small molecules in the human circulatory system contributes a lot to prompt personalized healthcare and early disease diagnose. The precise detection requires to select target molecules for real‐time noninvasive identifications, which remains a challenge derived from the lack of both molecule‐sieving techniques and rapid detection tools. Herein, positively charged polymer chains into graphene oxide membranes are seeded to tune their interlayer spacing precisely and persistently within a range of 8.67–13.75 Å. The adaptive yet stable nanocapillaries allow membranes to sieve small molecules with fitted sizes, for example, salts and biomarkers. The molecule‐sieving membranes with organic electrochemical transistors, further achieving an in vitro detection of lactate and uric acid with a high accuracy, are coupled. Based on this finding, a wearable sweat lactate rapid test kit, which detects sweat lactate secreted from human body within a few minutes, is demonstrated.

Taylor dispersion analysis using capacitively coupled contactless conductivity detector

Taylor dispersion analysis (TDA) is a simple and absolute method to determine the hydrodynamic radius of solutes that respond to UV or fluorescence detections. To broaden the application range of TDA, it is necessary to develop new detection modes. This study aims to study capacitively coupled contactless conductivity detector (C4D) for the analysis of charged macromolecules. The detection sensitivities and hydrodynamic radii were compared for a C4D detector and a UV detector on positively or negatively charged polymers responding both to UV and C4D (poly-L-lysine and poly(acrylamide-co-2-acrylamido-1-methyl-propanesulfonate). The influence of the composition of the background electrolyte on the detection sensitivity has been studied and optimized for C4D detection. The influence of the molar mass and of the polymer chemical charge density on the C4D and UV sensitivities of detection have been investigated based on well-characterized copolymers samples of different molar masses and charge densities. The advantages and disadvantages compared to UV detection, as well as the range of applicability of C4D detection in TDA were identified. C4D detection can be an alternative method for sizing charged polymers of reasonable molar mass (typically below 105 g mol−1) that do not absorb in UV. A decline in the sensitivity of detection in C4D was observed for higher molar masses.

Molecular Dynamics Simulations of Polyelectrolyte Complexes.

Polyelectrolyte complexes (PECs) are currently of great interest due to their applications toward developing new adaptive materials and their relevance in membraneless organelles. These complexes emerge during phase separation when oppositely charged polymers are mixed in aqueous media. Peptide-based PECs are particularly useful toward developing new drug delivery methods due to their inherent biocompatibility. The underlying peptide sequence can be tuned to optimize specific material properties of the complex, such as interfacial tension and viscosity. Given their applicability, it would be advantageous to understand the underlying sequence-dependent phase behavior of oppositely charged peptides. Here, we report microsecond molecular dynamic simulations to characterize the effect of hydrophobicity on the sequence-dependent peptide conformation for model polypeptide sequences that were previously reported by Tabandeh et al. These sequences are designed with alternating chirality of the peptide backbone. We present microsecond simulations of six oppositely charged peptide pairs, characterizing the sequence-dependent effect on peptide size, degree of hydrogen bonding, secondary structure, and conformation. This analysis recapitulates sensible trends in peptide conformation and degree of hydrogen bonding, consistent with experimentally reported results. Ramachandran plots reveal that backbone conformation at the single amino acid level is highly influenced by the neighboring sequence in the chain. These results give insight into how subtle changes in hydrophobic side chain size and chirality influence the strength of hydrogen bonding between the chains and, ultimately, the secondary structure. Furthermore, principal component analysis reveals that the minimum energy structures may be subtly modulated by the underlying sequence.

Efficient acid/alkali recovery enabled by only one negatively charged microporous polymer membrane

AbstractThe recovery of acid/base from industrial wastewater via membrane technology is energy efficient and has a low carbon footprint, while demanding high‐performing ion exchange membranes. It remains a grand challenge for ion exchange membranes, enabling concomitantly fast H+/OH− transport and high ion selectivity. This article presents a negatively charged microporous polymer membrane, a sulfonated polyxanthene membrane, which has intrinsic micropore channels for H+/OH− permeation, and we find that highly selective H+ and OH− transport can be acquired with the same membrane. This membrane exhibits a high H+/Fe2+ selectivity of 617 (6.3 times that of the commercial CIMS membrane) in acid recovery and a very high OH−/WO42− selectivity of 649 (the highest value ever reported) in alkali recovery while maintaining comparable H+/OH− transport rate. The results highlight the importance of hydrophilic micropores as ion‐selective channels in constructing high‐performing ion exchange membranes for resource recovery.

Coarse-Grained Model of Glycosaminoglycans for Biomolecular Simulations.

Proteoglycans contain glycosaminoglycans (GAGs) which are negatively charged linear polymers made of repeating disaccharide units of uronic acid and hexosamine units. They play vital roles in numerous physiological and pathological processes, particularly in governing cellular communication and attachment. Depending on their sulfonation state, acetylation, and glycosidic linkages, GAGs belong to different families. The high molecular weight, heterogeneity, and flexibility of GAGs hamper their characterization at atomic resolution, but this may be circumvented via coarse-grained (CG) approaches. In this work, we report a CG model for a library of common GAG types in their isolated or proteoglycan-linked states compatible with version 2.2 (v2.2) of the widely popular CG Martini force field. The model reproduces conformational and thermodynamic properties for a wide variety of GAGs, as well as matching structural and binding data for selected proteoglycan test systems. The parameters developed here may thus be employed to study a range of GAG-containing biomolecular systems, thereby benefiting from the efficiency and broad applicability of the Martini framework.

Self-Delivery Nanoplatform Based on Amphiphilic Apoptosis Peptide for Precise Mitochondria-Targeting Photothermal Therapy.

Mitochondria-targeting photothermal therapy could significantly enhance the tumor cell killing effect. However, since therapeutic reagents need to overcome a series of physiological obstacles to arrive at mitochondria accurately, precise mitochondria-targeting photothermal therapy still faces great challenges. In this study, we developed a self-delivery nanoplatform that specifically targeted the mitochondria of tumor cells for precise photothermal therapy. Photothermal agent IR780 was encapsulated by amphiphilic apoptotic peptide KLA with mitochondria-targeting ability to form nanomicelle KI by self-assembly through hydrophilic and hydrophobic interactions. Subsequently, negatively charged tumor-targeting polymer HA was coated on the surface of KI through electrostatic interactions, to obtain tumor mitochondria-targeting self-delivery nanoplatform HKI. Through CD44 receptor-mediated recognition, HKI was internalizated by tumor cells and then disassembled in an acidic environment with hyaluronidase in endosomes, resulting in the release of apoptotic peptide KLA and photothermal agent IR780 with mitochondria anchoring capacity, which achieved precise mitochondria guidance and destruction. This tumor mitochondria-targeting self-delivery nanoplatform was able to effectively deliver photothermal agents and apoptotic peptides to tumor cell mitochondria, resulting in precise destruction to mitochondria and enhancing tumor cell inhibition at the subcellular organelle level.

Ratiometric Imaging of Catecholamine Neurotransmitters with Nanosensors.

Neurotransmitters are important signaling molecules in the brain and are relevant in many diseases. Measuring them with high spatial and temporal resolutions in biological systems is challenging. Here, we develop a ratiometric fluorescent sensor/probe for catecholamine neurotransmitters on the basis of near-infrared (NIR) semiconducting single wall carbon nanotubes (SWCNTs). Phenylboronic acid (PBA)-based quantum defects are incorporated into them to interact selectively with catechol moieties. These PBA-SWCNTs are further modified with poly(ethylene glycol) phospholipids (PEG-PL) for biocompatibility. Catecholamines, including dopamine, do not affect the intrinsic E11 fluorescence (990 nm) of these (PEG-PL-PBA-SWCNT) sensors. In contrast, the defect-related E11* emission (1130 nm) decreases by up to 35%. Furthermore, this dual functionalization allows tuning selectivity by changing the charge of the PEG polymer. These sensors are not taken up by cells, which is beneficial for extracellular imaging, and they are functional in brain slices. In summary, we use dual functionalization of SWCNTs to create a ratiometric biosensor for dopamine.

Hydrogen Bonding Inside Anionic Polymeric Brush Layer: Machine Learning-Driven Exploration of the Relative Roles of the Polymer Steric Effect, Charging, and Type of Screening Counterions

Hydrogen Bonding Inside Anionic Polymeric Brush Layer: Machine Learning-Driven Exploration of the Relative Roles of the Polymer Steric Effect, Charging, and Type of Screening Counterions

Effect of moisture content on the triboelectric charging of polymers

The triboelectrostatic separation allows the sorting of granular polymers according to their contact charging characteristics. It consists in the appropriate triboelectric charging of particles, followed by their selective sorting in an electrostatic field. Exposed to a humid atmosphere, the polymer granules adsorb water moisture onto their surfaces, which modifies their charging characteristics, by improving the contact between surfaces. The present work was aimed at studying the effect of storage environmental conditions on the triboelectric charging of granular polymers in vibratory-type devices. Four granular different plastic wastes were placed in a climatic chamber and kept for 96 hours under controlled humidity, RH = 82% ± 4%, at 19 °C ± 1 °C. The measurement of the water content of the polymer granules pointed out an increase of at least 10% after 96 h of exposure to high relative humidity ambient conditions. The granules were successively charged by triboelectric effect in a vibratory device equipped with recipients in two different materials, at ambient conditions. The tribocharging efficiency was analyzed by measuring the electric charge of the granules with a Faraday pail connected to an electrometer. The thin water layer formed at the surface of the particle can explain their modified triboelectric behavior. The difference between the triboelectric charging behavior of “humid” and “normal” polymer granules depended also on the nature of the recipient of the tribocharging device.

Gold Nanoparticle-Decorated Polymer Particles for High-Optical-Density Immunoassay Probes.

To realize a highly sensitive immunoassay, high-optical-density probes conjugated with antibodies for target antigens are needed to increase the detectability of antigen-antibody complex formation. In this work, gold nanoparticle (NP)-decorated polymer (GNDP) particles were successfully prepared by mixing positively charged polymer particles and negatively charged Au NPs. GNDP particles decorated with NPs of 20 nm in size had higher optical density than the original Au NPs and GNDPs decorated with smaller Au NPs. Using GNDP particles as a probe, a highly sensitive immunoassay for influenza H1N1 hemagglutinin was realized with a minimum detectable concentration of 32.5 pg/mL. These results indicate that GNDP particles have high potential as an immunoassay probe that can be used in practical immunoassay systems for detecting a wide variety of antigens.