Influence of the backbone chemistry and ionic functional groups of five pairs of oppositely charged polyelectrolytes on complex coacervation.

Complex coacervation plays an important role in various fields. Here, the influences of the backbone chemistry and ionic functional groups of five pairs of oppositely charged polyelectrolytes on complex coacervation were investigated. These pairs include synthetic polymers with aliphatic hydrocarbon backbones, peptides with amide bonds, and carbohydrates with glycosidic linkages.

Anomalous diffusion of lithium-anion clusters in ionic liquids.

Lithium-ion transport is significantly retarded in ionic liquids (ILs). In this work, we performed extensive molecular dynamics simulations to mimic the kinetics of lithium ions in ILs using [N-methyl-N-propylpyrrolidium (pyr[Formula: see text])][bis(trifluoromethanesulfonyl)imide (Ntf[Formula: see text])] with added LiNtf[Formula: see text] salt. And we analyzed their transport, developing a two-state model and comparing it to the machine learning-identified states.

Martini Coarse-Grained Model of Hyaluronic Acid for the Structural Change of Its Gel in the Presence of Monovalent and Divalent Salts.

Hyaluronic acid (HA) has a wide range of biomedical applications including the formation of hydrogels, microspheres, sponges, and films. The modeling of HA to understand its behavior and interaction with other biomolecules at the atomic level is of considerable interest. The atomistic representation of long HA polymers for the study of the macroscopic structural formation and its interactions with other polyelectrolytes is computationally demanding.

Universality, Scaling, and Collapse in Supercritical Fluids.

Supercritical fluid (SCF) is known to exhibit salient dynamic and thermodynamic crossovers and an inhomogeneous molecular distribution. However, the question as to what basic physics underlies these microscopic and macroscopic anomalies remains open. Here, using an order parameter extracted by machine learning, the fraction of gas-like (or liquid-like) molecules, we find simplicity and universality in SCF: First, all isotherms of a given fluid collapse onto a single master curve described by a scaling relation.

Cation-π Interactions and Their Contribution to Mussel Underwater Adhesion Studied Using a Surface Forces Apparatus: A Mini-Review.

Mussel underwater adhesion is a model phenomenon important for the understanding of broader biological adhesion and the development of biomimetic wet adhesives. The catechol moiety of 3,4-dihydroxyphenyl-l-alanine (DOPA) is known to be actively involved in the mechanism of mussel underwater adhesion; however, other underwater adhesion mechanisms are also crucial. The surface forces apparatus (SFA) has often been used to explore the contributions of other mechanisms to mussel underwater adhesion; e.

Upper Critical Solution Temperature (UCST) Behavior of Coacervate of Cationic Protamine and Multivalent Anions.

Complex coacervation is an emerging liquid/liquid phase separation (LLPS) phenomenon that behaves as a membrane-less organelle in living cells. Yet while one of the critical factors for complex coacervation is temperature, little analysis and research has been devoted to the temperature effect on complex coacervation. Here, we performed a complex coacervation of cationic protamine and multivalent anions (citrate and tripolyphosphate (TPP)).

Salt Triggers the Simple Coacervation of an Underwater Adhesive When Cations Meet Aromatic π Electrons in Seawater.

Adhesive systems in many marine organisms are postulated to form complex coacervates (liquid-liquid phase separation) through a process involving oppositely charged polyelectrolytes. Despite this ubiquitous speculation, most well-characterized mussel adhesive proteins are cationic and polyphenolic, and the pursuit of the negatively charged proteins required for bulk complex coacervation formation internally remains elusive. In this study, we provide a clue for unraveling this paradox by showing the bulky fluid/fluid separation of a single cationic recombinant mussel foot protein, rmfp-1, with no additional anionic proteins or artificial molecules, that is triggered by a strong cation-π interaction in natural seawater conditions.

Molecular and structural basis of low interfacial energy of complex coacervates in water.

Complex coacervate refers to a phase-separated fluid, typically of two oppositely charged polyelectrolytes in solution, representing a complex fluid system that has been shown to be of essential interest to biological systems, as well as for soft materials processing owing to the expectation of superior underwater coating or adhesion properties. The significance and interest in complex coacervate fluids critically rely on its low interfacial tension with respect to water that, in turn, facilitates the wetting of macromolecular or material surfaces under aqueous conditions, provided there is attractive interaction between the polyelectrolyte constituents and the surface. However, the molecular and structural bases of these properties remain unclear.

Inositol pyrophosphates inhibit synaptotagmin-dependent exocytosis.

Inositol pyrophosphates such as 5-diphosphoinositol pentakisphosphate (5-IP7) are highly energetic inositol metabolites containing phosphoanhydride bonds. Although inositol pyrophosphates are known to regulate various biological events, including growth, survival, and metabolism, the molecular sites of 5-IP7 action in vesicle trafficking have remained largely elusive. We report here that elevated 5-IP7 levels, caused by overexpression of inositol hexakisphosphate (IP6) kinase 1 (IP6K1), suppressed depolarization-induced neurotransmitter release from PC12 cells.

Bicontinuous Fluid Structure with Low Cohesive Energy: Molecular Basis for Exceptionally Low Interfacial Tension of Complex Coacervate Fluids.

An exceptionally low interfacial tension of a dense fluid of concentrated polyelectrolyte complexes, phase-separated from a biphasic fluid known as complex coacervates, represents a unique and highly sought-after materials property that inspires novel applications from superior coating to wet adhesion. Despite extensive studies and broad interest, the molecular and structural bases for the unique properties of complex coacervates are unclear. Here, a microphase-separated complex coacervate fluid generated by mixing a recombinant mussel foot protein-1 (mfp-1) as the polycation and hyaluronic acid (HA) as the polyanion at stoichiometric ratios was macroscopically phase-separated into a dense complex coacervate and a dilute supernatant phase to enable separate characterization of the two fluid phases.

Chiral nematic self-assembly of minimally surface damaged chitin nanofibrils and its load bearing functions.

Chitin is one of the most abundant biomaterials in nature, with 10(10) tons produced annually as hierarchically organized nanofibril fillers to reinforce the exoskeletons of arthropods. This green and cheap biomaterial has attracted great attention due to its potential application to reinforce biomedical materials. Despite that, its practical use is limited since the extraction of chitin nanofibrils requires surface modification involving harsh chemical treatments, leading to difficulties in reproducing their natural prototypal hierarchical structure, i.

Complexation and coacervation of like-charged polyelectrolytes inspired by mussels.

It is well known that polyelectrolyte complexes and coacervates can form on mixing oppositely charged polyelectrolytes in aqueous solutions, due to mainly electrostatic attraction between the oppositely charged polymers. Here, we report the first (to the best of our knowledge) complexation and coacervation of two positively charged polyelectrolytes, which provides a new paradigm for engineering strong, self-healing interactions between polyelectrolytes underwater and a new marine mussel-inspired underwater adhesion mechanism. Unlike the conventional complex coacervate, the like-charged coacervate is aggregated by strong short-range cation-π interactions by overcoming repulsive electrostatic interactions.

Bundling in semiflexible polymers: A theoretical overview.

Supramolecular assemblies of polymers are key modules to sustain the structure of cells and their function. The main elements of these assemblies are charged semiflexible polymers (polyelectrolytes) generally interacting via a long(er)-range repulsion and a short(er)-range attraction. The most common supramolecular structure formed by these polymers is the bundle.

General Differential Contact Identities for Macromolecules.

We discuss general Maxwell identities relating a macromolecule's charge, the forces acting at its surface, and the osmotic pressure of the solution in which it sits. The identities are closely related to the contact value relations that hold for certain special geometries, but are more general. In particular, the Maxwell identities can be applied to any macromolecule geometry, and they hold both within and outside of mean-field theory.

Entangled polymer complexes as Higgs phenomena.

We derive an effective Maxwell-London equation for entangled polymer complexes under topological constraints, borrowing the theoretical framework from topological field theory. We find that the transverse current flux of a test polymer chain, surrounded by entangled chains, decays exponentially from its centerline position with a finite penetration depth, which is analogous to the magnetic-field decay in a superconductor (SC), referred to as the Meissner effect. Just as the mass acquirement of photons in a SC is the origin of the magnetic-field decay, the polymer obtains uncrossable intersections along the chain due to the preservation of the linking number, which restricts the deviation of the transverse polymer current in the normal direction.

Charge Renormalization for Ellipsoidal Macroions.

We study the problem of counterion condensation for ellipsoidal macroions, a geometry well-suited for modeling liquid crystals, anisotropic vesicles, and polymers. We find that the ions within an ellipsoid's condensation layer are relatively unrestricted in their motions, and consequently work to establish a quasi-equipotential at its surface. This simplifies the application of Alexander et al.

Cation-π interaction in DOPA-deficient mussel adhesive protein mfp-1.

Here we report the possible contribution of cation-π interaction to underwater adhesion of mussels by using DOPA-deficient recombinant mussel adhesive proteins. Considering the instability of DOPA in an oxidative environment, the cation-π interaction in DOPA-deficient biopolymers provides a complementary cross-linking mechanism for the design of novel underwater adhesives.

Electrostatic interaction between nonuniformly charged colloids: experimental and numerical study.

The influence of the surface charge distribution on the interaction between nanosized particles in water is reported. The distribution of charges at the surface of initially neutral microemulsion droplets has been modulated by additions of various oligomeric cationic surfactants. The osmotic compressibility of the doped microemulsions was measured by light and small-angle neutrons scattering and reveals that the overall effective interaction induced by the ionic groups is repulsive.

Contact time- and pH-dependent adhesion and cohesion of low molecular weight chitosan coated surfaces.

Low molecular weight chitosan (LMW chitosan, ∼5 kDa) potentially has many desirable biomedical applications such as anti-microbial, anti-tumor, and anti-diabetes. Unlike high molecular weight chitosan, LMW chitosan is easily dissolvable in aqueous solutions even at neutral and basic pH, but its dissolution mechanism is not well understood. Here, we measured adhesion and cohesion of molecularly thin LMW chitosan films in aqueous solutions in different buffer pHs (from 3.

Limiting law excess sum rule for polyelectrolytes.

We revisit the mean-field limiting law screening excess sum rule that holds for rodlike polyelectrolytes. We present an efficient derivation of this law that clarifies its region of applicability: The law holds in the limit of small polymer radius, measured relative to the Debye screening length. From the limiting law, we determine the individual ion excess values for single-salt electrolytes.

Repulsion between oppositely charged planar macroions.

The repulsive interaction between oppositely charged macroions is investigated using Grand Canonical Monte Carlo simulations of an unrestricted primitive model, including the effect of inhomogeneous surface charge and its density, the depth of surface charge, the cation size, and the dielectric permittivity of solvent and macroions, and their contrast. The origin of the repulsion is a combination of osmotic pressure and ionic screening resulting from excess salt between the macroions. The excess charge over-reduces the electrostatic attraction between macroions and raises the entropic repulsion.