Polyelectrolyte Complex Coacervates Research Articles

A Jacobian-free pseudo-arclength continuation method for phase transitions in inhomogeneous thermodynamic systems.

Developing phase diagrams for inhomogeneous systems in thermodynamics is difficult, in part, due to the large phase space and the possibility of unstable and metastable solutions arising from first-order phase transitions. Pseudo-arclength continuation (PAC) is a method that allows one to trace out stable and unstable solutions of nonlinear systems. Typically, PAC utilizes the Jacobian in order to implement Newton (or quasi-Newton) steps. In this work, we present a Jacobian-free PAC method that is amenable to the usual workflows in inhomogeneous thermodynamics. We demonstrate our method in systems that have first-order phase transitions, including a novel example of polyelectrolyte complex coacervation in confinement, where multiple surface phase transitions occur and can overlap with one another.

Chitosan‒gellan gum polyelectrolyte hydrogel beads containing tea tree oil microcapsules: Preparation, characterization and application

Encapsulation can be applied for essential oil protection, increasing the probability of its application in food preservation. In this study, tea tree oil (TTO) microcapsule powder (MP) was prepared by a spray‒drying approach with soy protein isolate (SPI) and fructooligosaccharide (FOS) as wall materials and were subsequently further encapsulated by chitosan (CH) and gellan gum (GG) via a polyelectrolyte complex coacervation approach. The hydrogel beads prepared with a GG mass ratio of 25% presented the best appearance and the densest internal structure. FTIR and Raman spectral analyses demonstrated the generation of hydrogen bonds between CH and GG. Thermogravimetric analysis confirmed that complex coacervates formed by CH and GG as wall materials can improve the thermal stability of TTO. Owing to the excellent barrier properties of the hydrogel beads, the hydrogel beads maintained high DPPH and ABTS free radical scavenging activities after storage. Moreover, the sustained release of TTO hydrogel beads has potential for preserving fresh-cut banana. These discoveries indicate that hydrogel beads can be used as ideal carriers of essential oils such as TTO and may be used in food preservation in the future.

Comprehensive Dynamics in a Polyelectrolyte Complex Coacervate

Comprehensive Dynamics in a Polyelectrolyte Complex Coacervate

Polyelectrolyte nanocomplex from sodium caseinate and chitosan as potential vehicles for oil encapsulation by flash nanoprecipitation

A polyelectrolyte complex coacervation technique has been used for emulsion stabilization, nutraceutical encapsulation, and controlled delivery. However, traditional batch-mixing methods suffer from significant insufficiencies in scalability because of batch-to-batch variation and complicated multi-step preparation procedures resulting in uncontrollable size, wide size distribution, instability, and aggregation. This study used a flash nanocomplexation (FNC) method to continuously prepare protein (sodium caseinate) and polysaccharide (chitosan) nanocomplexes with narrow size distributions using a multi-inlet vortex mixer. The size distributions of nanocomplex can be controlled by volumetric flow rates of the inlet streams, the concentration, and the order/ratio of sodium caseinate to chitosan. Furthermore, a novel emulsion preparation method, flash-microemulsion (FME), was introduced. Under rapid mixing conditions, FME prepared emulsion in the presence of soybean or MCT oil by infusing aqueous solutions of sodium caseinate and chitosan in a single step. O/W emulsion prepared successfully by the FME method was confirmed with confocal microscopy. The emulsion droplet size ranged from 4.6 to 1.5 μm and showed elastic-like properties (G' > G″). Optical microscope, SEM, and TEM studies suggested that the FME method could form homogeneous and stable emulsions. The emulsions showed excellent stability over 30 days of storage. In addition, there were no noticeable differences in the size and size distribution of nanocomplex and emulsion prepared at different times, indicating excellent reproducibility. As a result of FNC and FME, other lipophilic bioactive compounds can be encapsulated/stabilized in the food, flavor, pharmaceutical, and cosmetic industries.

Charge Asymmetry Suppresses Coarsening Dynamics in Polyelectrolyte Complex Coacervation

Charge Asymmetry Suppresses Coarsening Dynamics in Polyelectrolyte Complex Coacervation

Effects of Control Factors on Protein-Polyelectrolyte Complex Coacervation.

Protein-polyelectrolyte complex coacervation is of particular interest for mimicking intracellular phase separation and organization. Yet, the challenge arises from regulating the coacervation due to the globular structure and anisotropic distributed charges of protein. Herein, we fully investigate the different control factors and reveal their effects on protein-polyelectrolyte coacervation. We prepared mixtures of BSA (bovine serum albumin) with different cationic polymers, which include linear and branched polyelectrolytes covering different spacer and charge groups, chain lengths, and polymer structures. With BSA-PDMAEMA [poly(N,N-dimethylaminomethyl methacrylate)] as the main investigated pair, we find that the moderate pH and ionic strength are essential for the adequate electrostatic interaction and formation of coacervate droplets. For most BSA-polymer mixtures, excess polyelectrolytes are required to achieve the full complexation, as evidenced by the deviated optimal charge mixing ratios from the charge stoichiometry. Polymers with longer chains or primary amine groups and a branched structure endow a strong electrostatic interaction with BSA and cause a bigger charge ratio deviation associated with the formation of solid-like coacervate complexes. Nevertheless, both the liquid- and solid-like coacervates hardly interrupt the BSA structure and activity, indicating the safe encapsulation of proteins by the coacervation with polyelectrolytes. Our study validates the crucial control of the diverse factors in regulating protein-polyelectrolyte coacervation, and the revealed principles shall be instructive for establishing other protein-based coacervations and boosting their potential applications.

Strong tissue adhesive polyelectrolyte complex powders based on low molecular weight chitosan for acute hemorrhage control

Self-gelling and bioadhesive powders offered promising effective hemostats to suit irregularly shaped, complex and non-compressible wounds for clinical applications. In the current study, chitosan based polyelectrolyte complex coacervate were simply prepared by mixing high concentrations (10 %) of low molecular weight chitosan (CS) and polyacrylic acid (PAA) solutions. Obtained by lyophilization, the physical cross-linked polyelectrolyte complex powders would form a gel within 5 s upon hydration, which demonstrated excellent mechanical properties, significant antibacterial activities, strong and lasting adhesion on wet tissues in physiological environment. In vitro blood clotting assays showed that the CS/PAA powders could remarkably aggregate blood cells and accelerate blood clotting process. As studied by diverse hemorrhage models, including rat tail, liver and heart injuries and dog incision, CS/PAA powders significantly facilitated the decrease of blood loss as well as hemostatic time by creating robust physical barriers and promoting blood clot formation on the bleeding sites. These outstanding properties in terms of easy preparation, rapid self-gelling, strong wet adhesion, effective hemostasis and shape-adaptability endowed CS/PAA polyelectrolyte complex powders with great potential in managing acute hemorrhage of non-compressible trauma.

Coacervate or precipitate? Formation of non-equilibrium microstructures in coacervate emulsions.

Non-equilibrium processing of aqueous polyelectrolyte complex (PEC) coacervates is critical to many applications. In particular, many coacervate-forming systems are known to become trapped in out-of-equilibrium states (e.g., precipitation). The mechanism and conditions under which these states form, and whether they age, is not clearly understood. Here, we elucidate the influence of processing on the PEC coarsening mechanism as it varies with flow during mixing for a model system of poly(allylamine hydrochloride) and poly(acrylic acid sodium salt) in water. We demonstrate that flow conditions can be used to toggle the formation of rough, precipitate-like aggregates of micron-scale PEC structures. These structures form at compositions with viscous-dominant equilibrium rheology, and observations of their formation via optical microscopy suggest that they comprise colloidal aggregates of PEC coacervate droplets. We further show that these aggregates exhibit micron-scale coarsening, with a mixing time-dependent characteristic aging time scale. The results show that the formation of precipitate-like structures is not solely determined by composition, but is instead highly sensitive to mass transport and colloidal instability effects. Our observations suggest that the details of mixing flow can provide non-equilibrium structural control of a broad range of PEC coacervate materials orthogonally to structure-property inspired polymeric design. We anticipate that these findings will open the door for future studies on the control of non-equilibrium PEC formation and structure.

Driving force and pathway in polyelectrolyte complex coacervation

There is notable discrepancy between experiments and coarse-grained model studies regarding the thermodynamic driving force in polyelectrolyte complex coacervation: experiments find the free energy change to be dominated by entropy, while simulations using coarse-grained models with implicit solvent usually report a large, even dominant energetic contribution in systems with weak to intermediate electrostatic strength. Here, using coarse-grained, implicit-solvent molecular dynamics simulation combined with thermodynamic analysis, we study the potential of mean force (PMF) in the two key stages on the coacervation pathway for symmetric polyelectrolyte mixtures: polycation-polyanion complexation and polyion pair-pair condensation. We show that the temperature dependence in the dielectric constant of water gives rise to a substantial entropic contribution in the electrostatic interaction. By accounting for this electrostatic entropy, which is due to solvent reorganization, we find that under common conditions (monovalent ions, room temperature) for aqueous systems, both stages are strongly entropy-driven with negligible or even unfavorable energetic contributions, consistent with experimental results. Furthermore, for weak to intermediate electrostatic strengths, this electrostatic entropy, rather than the counterion-release entropy, is the primary entropy contribution. From the calculated PMF, we find that the supernatant phase consists predominantly of polyion pairs with vanishingly small concentration of bare polyelectrolytes, and we provide an estimate of the spinodal of the supernatant phase. Finally, we show that prior to contact, two neutral polyion pairs weakly attract each other by mutually induced polarization, providing the initial driving force for the fusion of the pairs.

Influence of “Hydrophobicity” on the Composition and Dynamics of Polyelectrolyte Complex Coacervates

Various types of specific interactions are believed to supplement the major entropic driving forces responsible for spontaneous liquid–liquid phase separations in mixtures of oppositely charged polyelectrolytes. Among these interactions, hydrophobicity has recently been probed experimentally via the synthesis and complex formation of polyelectrolytes bearing hydrophobic pendant groups or backbones. In this work, poly(4-vinylpyridines), P4VP, were N-alkylated with chains from one to six carbons in length. The fully alkylated polycations were complexed with poly(sodium methacrylate) to yield polyelectrolyte complexes or coacervates (PECs). Counterintuitively, PECs made with N-methyl to N-butyl P4VP were less stable to the addition of salt the longer the alkane chain, being easier to dope and having a lower critical salt concentration for dissolution. In contrast, the linear viscoelastic response of these PECs varied little. A transition in doping and properties was observed with N-pentyl and N-hexyl chains, the latter having a much higher modulus and much less sensitivity to salt concentration. Small-angle X-ray scattering suggested a new morphology for the N-pentyl and N-hexyl P4VP PECs, with interacting/phase separating alkane chains providing a transition into hydrophobicity-dominated PECs.

Complexation between Oppositely Charged Polyelectrolytes in Dilute Solution: Effects of Charge Asymmetry

We use dissipative particle dynamics to study polyelectrolyte complexation in dilute solutions under conditions of either chain-length or concentration asymmetry between the polycation and the polyanion, characterized by the macromolecular charge ratio of the minor component to the major component. Our results show that generally the systems form clusters carrying net macromolecular charges. The stoichiometry of these net-charged macromolecular clusters depends on the overall charge asymmetry, and clusters with certain stoichiometry can dominate the cluster population under a wide range of chain-length and concentration asymmetry. The morphology and stability of these net-charged clusters are closely related to their stoichiometry. When the charge ratio reaches a threshold value, the polyions condense into a single large coacervate cluster, signaling the onset of macroscopic coacervation. The threshold value is less for concentration asymmetry systems than for chain-length asymmetry systems at the same salt concentration. This threshold value decreases with added salt, as salt ions cause merging of small clusters into larger ones, eventually leading to the dominance of a single large cluster. This “salting-out” phenomenon is followed by a “salting-in” behavior, as further addition of salt dissolves the large cluster. The preferred size and composition of the net-charged clusters observed in the simulation highlight the significant role of length and concentration asymmetry on polyelectrolyte complex coacervation and hint at the possibility of a microstructured liquid.

Supernatant Phase in Polyelectrolyte Complex Coacervation: Cluster Formation, Binodal, and Nucleation

Supernatant Phase in Polyelectrolyte Complex Coacervation: Cluster Formation, Binodal, and Nucleation

Inspired by mussel: biomimetic polyelectrolyte complex coacervate adhesive initiates a connection through water exchange

Here the authors report a versatile and strong underwater adhesive that was inspired by the chemical features of mussel foot proteins. A random copolymer (poly(N-(3,4-dihydroxyphenethyl)methacrylamide-co-methacryloxyethyltrimethyl ammonium chloride-co-acrylamide) (PDMA)–Tf2N) was prepared that contained side-chain catechol groups and quaternary ammonium cations that were ion-paired with bis(trifluoromethane-sulfonyl)imide anion (Tf2N−). After dissolving PDMA–Tf2N and poly(acrylic acid) in dimethyl sulfoxide, a polyelectrolyte complex coacervate adhesive (P2) could be formed, which could be triggered through solvent exchange. P2 exhibited outstanding underwater shear strength to various substrate surfaces. After a critical curing time (t s = 10 min), the adhesion strength of P2 to glass increased sharply up to 187.298 kPa (t s = 40 min).

Wetting behavior of polyelectrolyte complex coacervates on solid surfaces.

The wetting behavior of complex coacervates underpins their use in many emerging applications of surface science, particularly wet adhesives and coatings. Many factors dictate if a coacervate phase will condense on a solid surface, including solution conditions, the nature of the polymer-substrate interaction, and the underlying supernatant-coacervate bulk phase behavior. In this work, we use a simple inhomogeneous mean-field theory to study the wetting behavior of complex coacervates on solid surfaces both off-coexistence (wetting transitions) and on-coexistence (contact angles). We focus on the effects of salt concentration, the polycation/polyanion surface affinity, and the applied electrostatic potential on the wettability. We find that the coacervate generally wets the surface via a first order wetting transition with second order transitions possible above a surface critical point. Applying an electrostatic potential to a solid surface always improves the surface wettability when the polycation/polyanion-substrate interaction is symmetric. For asymmetric surface affinity, the wettability has a nonmonotonic dependence with the applied potential. We use simple scaling and thermodynamic arguments to explain our results.

Correction to “Lower Critical Solution Temperature in Polyelectrolyte Complex Coacervates”

ADVERTISEMENT RETURN TO ISSUEPREVCorrectionNEXTORIGINAL ARTICLEThis notice is a correctionCorrection to “Lower Critical Solution Temperature in Polyelectrolyte Complex Coacervates”Samim AliSamim AliMore by Samim Alihttps://orcid.org/0000-0002-4607-0210, Markus BleuelMarkus BleuelMore by Markus Bleuel, and Vivek M. Prabhu*Vivek M. PrabhuMore by Vivek M. Prabhuhttps://orcid.org/0000-0001-8790-9521Cite this: ACS Macro Lett. 2021, 10, 12, 1636Publication Date (Web):December 6, 2021Publication History Received22 November 2021Published online6 December 2021Published inissue 21 December 2021https://doi.org/10.1021/acsmacrolett.1c00727Copyright © 2021 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views531Altmetric-Citations1LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (453 KB) Get e-AlertsSUBJECTS:Polymer solutions,Anions,Physical and chemical properties,Polyelectrolytes,Polymers Get e-Alerts

Interfacial Structure and Tension of Polyelectrolyte Complex Coacervates

We develop a simple inhomogeneous mean-field theory to study the interfacial structure and tension of polyelectrolyte complex coacervates in equilibrium with a supernatant solution. Our theory treats the electrostatic correlation by combining the Debye–Hückel theory with the first-order thermodynamic perturbation theory within the local density approximation, and incorporates the conformation entropy contribution for both polyions using Lifshitz’s ground-state dominance approximation. Using this theory, we systematically examine the interfacial properties of both symmetric and concentration-asymmetric coacervates. The interfacial tension γ is generally rather low, on the order of 1 mN/m or less. For asymmetric coacervates, an intricate electric double layer forms in the interfacial region, which can even contain several oscillations under certain conditions. The interfacial tension generally decreases with increasing the stoichiometric asymmetry, the added-salt concentration, and the initial polymer concentration of the mixture. We further find that the interfacial tension can be quantitatively related to the degree of phase separation S, where S is the Euclidean distance in composition between the two coexisting phases. In particular, we find that γ as a function of S for different concentration asymmetries collapses approximately to two master curves, which merge together and follow γ ∼ S3 for small S.

Preparation of Poly(acrylate)/Poly(diallyldimethylammonium) Coacervates without Small Counterions and Their Phase Behavior upon Salt Addition towards Poly-Ions Segregation.

In this work, we report the phase behavior of polyelectrolyte complex coacervates (PECs) of poly(acrylate) (PA−) and poly(diallyldimethylammonium) (PDADMA+) in the presence of inorganic salts. Titrations of the polyelectrolytes in their acidic and alkaline forms were performed to obtain the coacervates in the absence of their small counterions. This approach was previously applied to the preparation of polymer–surfactant complexes, and we demonstrate that it also succeeded in producing complexes free of small counterions with a low extent of Hofmann elimination. For phase behavior studies, two different molar masses of poly(acrylate) and two different salts were employed over a wide concentration range. It was possible to define the regions at which associative and segregative phase separation take place. The latter one was exploited in more details because the segregation phenomenon in mixtures of oppositely charged polyelectrolytes is scarcely reported. Phase composition analyses showed that there is a strong segregation for both PA− and PDADMA+, who are accompanied by their small counterions. These results demonstrate that the occurrence of poly-ion segregation in these mixtures depends on the anion involved: in this case, it was observed with NaCl, but not with Na2SO4.

Polyelectrolyte Complex Coacervation across a Broad Range of Charge Densities

Polyelectrolyte complex coacervates of homologous (co)polyelectrolytes with a near-ideally random distribution of a charged and neutral ethylene oxide comonomer were synthesized. The unique platform provided by these building blocks enabled an investigation of the phase behavior across charge fractions 0.10 ≤ f ≤ 1.0. Experimental phase diagrams for f = 0.30–1.0 were obtained from thermogravimetric analysis of complex and supernatant phases and contrasted with molecular dynamics simulations and theoretical scaling laws. At intermediate to high f, a dependence of polymer weight fraction in the salt-free coacervate phase (wP,c) of wP,c ∼ f0.37±0.01 was extracted; this trend was in good agreement with accompanying simulation predictions. Below f = 0.50, wP,c was found to decrease more dramatically, qualitatively in line with theory and simulations predicting an exponent of 2/3 at f ≤ 0.25. Preferential salt partitioning to either coacervate or supernatant was found to be dictated by the chemistry of the constituent (co)polyelectrolytes.

Cationic Polyelectrolyte Nanocapsules of Moxifloxacin for Microbial Keratitis Therapy: Development, Characterization, and Pharmacodynamic Study.

Microbial keratitis (MK) is a vision-threatening disease and the fourth leading cause of blindness worldwide. In this work, we aim to develop moxifloxacin (MXN)-loaded chitosan-based cationic mucoadhesive polyelectrolyte nanocapsules (PENs) for the effective treatment of MK. PENs were formulated by polyelectrolyte complex coacervation method and characterized for their particle size, surface charge, morphology, mucoadhesive property, in-vitro and ex-vivo release, ocular tolerance, and antimicrobial efficacy studies. The pharmacodynamic study was conducted on rabbit eye model of induced keratitis and it is compared with marketed formulation (MF). Developed PENs showed the size range from 230.7 ± 0.64 to 249.0 ± 0.49 nm and positive surface charge, spherical shape along with appropriate physico-chemical parameters. Both in-vitro and ex-vivo examination concludes that PENs having more efficiency in sustained release of MXN compared to MF. Ocular irritation studies demonstrated that no corneal damage or ocular irritation. The in-vivo study proved that the anti-bacterial efficacy of PENs was improved when compared with MF. These results suggested that PENs are a feasible choice for MK therapy because of their ability to enhance ocular retention of loaded MXN through interaction with the corneal surface of the mucous membrane.

The Structure of Polyelectrolyte Complex Coacervates and Multilayers

The equilibrium structure of the polyelectrolyte (PE) complex coacervates and homogeneous multilayers formed by polycations and polyanions with incompatible backbones in a poor solvent is studied u...