Article
Chemistry, Physical
Frances J. Morin, Marissa L. Puppo, Jennifer E. Laaser
Summary: Changes in salt concentration and polymer concentration in polyelectrolyte complex coacervates are typically strongly coupled, complicating the interpretation of the dynamics of these materials. A new salt addition method was developed to prepare coacervates with varying salt concentrations while keeping polymer concentration constant. Characterization of these samples revealed a stronger correlation between relaxation times and polymer volume fraction than previously assumed, emphasizing the importance of considering both salt and polymer-dependent contributions to the dynamics of complex materials.
Article
Polymer Science
Jun Huang, Jennifer E. Laaser
Summary: The role of hydrophobicity, particularly of nonionic hydrophobic comonomers, in the phase behavior of polyelectrolyte complex coacervates was explored by synthesizing a library of polymers with varying charge densities and nonionic hydrophobic side chain lengths. Turbidity measurements revealed a complex salt response with distinct charge density-dominated and hydrophobicity-dominated regimes, indicating the difficulty of understanding the coacervate phase behavior solely based on polymer-water interactions. This suggests further research is needed to understand how specific molecular-scale interactions moderate the phase behavior of complex coacervates.
Article
Polymer Science
Sojeong Kim, Won Bo Lee, Nicolas R. de Souza, Soo-Hyung Choi
Summary: The segmental dynamics of complex coacervates were studied using quasi-elastic neutron scattering. It was found that the number of mobile chain segments and their dynamics increase with salt concentration in ammonium-based coacervates, whereas guanidinium-based coacervates show slow and comparable segmental relaxation regardless of salt concentration, possibly due to non-electrostatic interactions. The combination of chemical structure, salt concentration, and temperature plays a significant role in determining polymer chain dynamics influenced by the strength of ionic bonding.
Article
Polymer Science
Xiangxi Meng, Yifeng Du, Yalin Liu, E. Bryan Coughlin, Sarah L. Perry, Jessica D. Schiffman
Summary: This study demonstrates for the first time that linear, nonentangled oligomeric polyelectrolytes can be electrospun into fibers. By using the complex coacervation phenomenon, the electrospinning efficiency was significantly improved compared to traditional studies investigating polymer solution parameters.
Article
Polymer Science
Wesam A. A. Hatem, Yakov Lapitsky
Summary: Mechanical stimulation can accelerate the release of small molecules from complex coacervates and result in a deswelling effect. The mechanical activation effect is most pronounced in water and only subtle and short-lived in phosphate buffered saline.
Article
Chemistry, Multidisciplinary
Jere van Lente, Monica Pazos Urrea, Thomas Brouwer, Boelo Schuur, Saskia Lindhoud
Summary: Various solvents have been suggested as greener alternatives to existing extraction processes, and macroscopic complex coacervates are proposed as a new addition to this list. These complex coacervates, liquid-like forms of polyion condensates, have the ability to extract certain solutes from water and back-extract them by changing parameters. The distribution coefficients of industrial chemicals in poly(ethylenimine)/poly(acrylic acid) complex coacervates can vary strongly depending on tunable parameters like polyion ratio, ionic strength, and temperature, showing potential as extraction media.
Article
Polymer Science
Julien Es Sayed, Cleïment Caito, Abinaya Arunachalam, Armin Amirsadeghi, Larissa van Westerveld, Denise Maret, Roshan Akdar Mohamed Yunus, Eleonora Calicchia, Olivia Dittberner, Giuseppe Portale, Daniele Parisi, Marleen Kamperman
Summary: Complex coacervates are versatile materials formed by electrostatic associations between polyelectrolytes. The viscoelastic properties of these materials can be easily altered by the ionic strength of the medium, resulting in a range of materials from liquids to gels. This study reveals the importance of intermolecular hydrogen bonds on the phase behavior and viscoelasticity of HA-CHI complex coacervates. The density of hydrogen bonds between CHI units increases with pH, leading to elastic gel-like behavior. This pH-dependent behavior is relevant for the design of polyelectrolyte materials.
Article
Chemistry, Physical
Larissa van Westerveld, Julien Es Sayed, Marijn de Graaf, Anton H. Hofman, Marleen Kamperman, Daniele Parisi
Summary: The rheology of complex coacervates can be finely tuned by manipulating specific non-covalent hydrophobic interactions between the polymer chains. This study introduces a method to control the hydrophobicity of the polymer chains in complex coacervates, allowing for the prediction of rheology and the optimization of aqueous pressure-sensitive adhesive (PSA) systems.
Article
Polymer Science
Philipp Schroeder, Monika Schoenhoff, Cornelia Cramer
Summary: Complex coacervates of chitosan and gum arabic, two naturally abundant weak polyelectrolytes, were studied using oscillatory shear rheology. The results showed that the shear moduli scaled with temperature, salt concentration, and pH, indicating the applicability of time-temperature superposition (TTSP), time-salt superposition (TSSP), and time-pH superposition (TpHSP). However, a breakdown of superposition occurred in the low-frequency regime at high salt concentrations and pH values near the pK (a) of chitosan. This breakdown was attributed to gelation, likely due to the associative interaction of chitosan chains and the formation of a chitosan network.
Article
Chemistry, Physical
Anna R. Johnston, Gregory M. Pitch, Eris D. Minckler, Ivette G. Mora, Vitor H. Balasco Serrao, Eric A. Dailing, Alexander L. Ayzner
Summary: This article introduces a conjugated polyelectrolyte that can undergo liquid/liquid phase separation in water, and discusses the behavior of excitonic states in the liquid coacervate phase. This research is significant for understanding liquid/liquid phase separation and for potential applications in light harvesting.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Biochemistry & Molecular Biology
Philipp Schroeder, Stefan Cord-Landwehr, Monika Schoenhoff, Cornelia Cramer
Summary: This study investigates the composition and charge compensation of complex coacervates of chitosan and gum arabic, depending on pH and salt concentration. The individual polyelectrolyte yields were determined using thermogravimetric analysis and enzymatic hydrolysis/HPLC-ELSD for chitosan quantification. The mass ratio of polyelectrolytes in the complex coacervate remains constant regardless of pH, with either chitosan or gum arabic charges in excess depending on pH. The amount of extrinsic charge compensation in the complex coacervate is discussed, and the doping level is found to be suitable for describing pH-induced extrinsic charge compensation in such systems.
Review
Mechanics
Ronald G. Larson, Ying Liu, Huiling Li
Summary: The linear viscoelasticity of coacervates formed by oppositely charged polyelectrolytes in salt solution is reviewed, focusing on time-temperature, time-salt, time-pH, and time-hydration superpositions, as well as fundamental relaxation mechanisms. It is found that while the time-salt superposition is frequently successful in various polyelectrolyte pairs, it is not universal.
JOURNAL OF RHEOLOGY
(2021)
Article
Mechanics
Huiling Li, Ying Liu, Abhishek Shetty, Ronald G. G. Larson
Summary: A comprehensive study was conducted on the salt concentration and polymer chain lengths dependencies of the low-frequency plateau in coacervates of poly (diallyl dimethyl ammonium chloride), PDADMAC, and poly (sodium 4-styrenesulfonate), PSS. The reliability and reproducibility of the measurements were carefully verified, and it was found that coacervates with less salt exhibited greater repeatability. The appearance and magnitude of the low-frequency plateau were strongly influenced by the salt concentration and chain lengths of both the polycation and polyanion.
JOURNAL OF RHEOLOGY
(2022)
Article
Biochemistry & Molecular Biology
Shanta Biswas, Alison L. Hecht, Sadie A. Noble, Qingqiu Huang, Richard E. Gillilan, Amy Y. Xu
Summary: This study investigates the effects of crowding on a model protein-polymer complex coacervate system. The presence of crowders, sucrose and PEG, led to the formation of larger and more stable coacervate droplets. Sucrose had minimal effects on the physical properties of the coacervates, while PEG influenced the coacervate characteristics, resulting in higher density, increased content, and a more compact internal structure. Additionally, sucrose was present in both the coacervate and dilute phases, while PEG was excluded from the coacervate phase.
Review
Chemistry, Physical
Tiemei Lu, Sadaf Javed, Claudia Bonfio, Evan Spruijt
Summary: Compartmentalization is vital for cell function, with membranes providing protection, regulation, and organization. Membraneless condensates also play important roles, facilitating interactions with cellular membranes and contributing to various cellular processes. These interactions have potential applications in artificial cells, as demonstrated by recent studies involving coacervates and liposomes. Different functions, such as acting as artificial organelles, membrane templates, remodelers, and cargo containers, can be achieved based on the size and interaction strength between coacervates and membranes. This review discusses experimental examples, underlying principles, and future applications.