Phase-separated Polymer Research Articles

A Multiscale Perspective on Chromatin Architecture through Polymer Physics.

The spatial organization of chromatin within the eukaryotic nucleus is critical in regulating key cellular functions, such as gene expression, and its disruption can lead to disease. Advances in experimental techniques, such as Hi-C and microscopy, have significantly enhanced our understanding of chromatin's intricate and dynamic architecture, revealing complex patterns of interaction at multiple scales. Along with experimental methods, physics-based computational models, including polymer phase separation and loop-extrusion mechanisms, have been developed to explain chromatin structure in a principled manner. Here, we illustrate genome-wide applications of these models, highlighting their ability to predict chromatin contacts across different scales and to spread light on the underlying molecular determinants. Additionally, we discuss how these models provide a framework for understanding alterations in chromosome folding associated with disease states, such as SARS-CoV-2 infection and pathogenic structural variants, providing valuable insights into the role of chromatin architecture in health and disease.

Photonics of High-Entropy Polymers Revealing Molecular Dispersion via Polymer Mixing.

Blending multiple polymers together to form the so-called "high-entropy polymers (HEPs)" can generate the effects of molecular dispersion in addition to suppressing polymer phase separation. We embedded a semiconducting polymer (conjugated polymers, CPs) in an optically inert matrix composed of n polymer species and found that a molecule-level dispersion is attained in HEPs defined as n ≥ 5. In the regime of dilute CP concentrations, the photonic properties vary widely in the n = 1 matrices owing to diverse solubility parameters, but the distribution narrows with n, and the CP starts to exhibit behaviors of molecule-level dispersion at n ≥ 5, where the matrix polymers compete with each other to exert direct influences on the embedded CP. Specifically, for MEH-PPV, increasing n reduces the fluorescence redshift and spectral width from diminishing aggregation. For the rigid PFO molecules, increasing n creates a dilution effect facilitating formation of the low-energy planar β-phase. For the flexible regioregular P3HT-rr, HEPs offer well-dispersed amorphous chains highly susceptible to chain environments, thus influencing ηR's in the quasi-fixed amorphous-crystalline energy transfer landscape. The HEP effects continue for greater CP concentrations, consistent with the matrix dispersing behaviors in the dilute regime. This work demonstrates a molecular-level dispersion by HEPs, offering a method of molecular tailoring for polymer research and applications via simple mixing.

Phase-separated polymer blends for controlled drug delivery by tuning morphology

Controlling drug release rate and providing physical and chemical stability to the active pharmaceutical ingredient are key properties of oral solid dosage forms. Here, we demonstrate a formulation strategy using phase-separated polymer blends where the morphology provides a route for tuning the drug release profile. By utilising phase separation of a hydrophobic and a hydrophilic polymer, the hydrophilic component will act as a channelling agent, creating a porous network upon dissolution that will dictate the release characteristics. With ptychographic X-ray tomography and scanning transmission X-ray microscopy we reveal how the morphology depends on both polymer fraction and presence of drug, and how the drug is distributed over the polymer domains. Combining X-ray imaging results with dissolution studies reveal how the morphologies are correlated with the drug release and showcase how tuning the morphology of a polymer matrix in oral formulations can be utilised as a method for controlled drug release.

Low-voltage operatable top-gated organic transistors based on the solution-processed binary polymers dielectric for simplifying the manufacturing flow of arrayed AMOLED

The complex process flow is an important factor that hinders the development of active-matrix organic light-emitting diode (AMOLED) displays. Organic thin-film transistors (OTFTs) are one of the promising candidates as the pixel circuits for AMOLEDs. Both the architecture and the fabrication of OTFTs are crucial elements to determine the process flow and cost of the AMOLEDs. In this Letter, we develop a strategy to significantly simplify the process flow and reduce the cost of AMOLEDs by constructing top-gated OTFTs with a solution-processed vertically phase separated binary polymer dielectric as the pixel circuits. The design on the OTFTs considers both the process flow and the device performance in terms of mobility and operating voltages. The mechanism to improve device performances is discussed. Finally, a 3 × 4 arrayed AMOLED is demonstrated, in which a high mobility over 0.3 cm2/Vs is obtained on the switching and driving OTFTs, and luminance over 300 cd/m2 is achieved on the OLEDs at the supplied low operating voltages of 10 V. This strategy provides a competitive technological route for the manufacturing of AMOLEDs.

AFM-IR Spectromicroscopy Unveils Hidden Phase Separation in Polymer–Polymer Blend Films for Photovoltaic Applications

AFM-IR Spectromicroscopy Unveils Hidden Phase Separation in Polymer–Polymer Blend Films for Photovoltaic Applications

The phase field method coupled with molecular dynamics parameter for simulating phase separation behavior of SBS modified asphalt

Polymer-modified asphalt is a thermodynamically unstable system, in which the polymer and asphalt are prone to phase separation. Due to the inadequacy of characterization methods for phase separation, this field has not been thoroughly understood or explored. This paper introduces an innovative methodology by employing a simulation approach that couples phase-field theory with molecular dynamics parameters. Using SBS polymer-modified asphalt as an example, validate the method's applicability and establish a more precise parameter library for the phase separation field model of SBS-modified asphalt. The phase separation process of SBS-modified asphalt was simulated. In combination with fluorescence microscopy experiments, the evolution of the micro and meso-phase states of the modified asphalt over time was established and tracked. Results indicate that higher light component content and lower heavy component content in asphalt improve its compatibility. Migration coefficients and interaction parameters for the phase field model were determined, and a more accurate correction factor for the entropy contribution of SBS-modified asphalt was estimated. The phase-field model shows that higher light component content and lower heavy component content result in slower and smaller phase separation, leading to better compatibility. The combined phase field and molecular dynamics simulations accurately reproduce experimental findings from fluorescence microscopy, providing theoretical references for studying phase separation in polymers.

Shape memory and mechanical properties of ESO modified epoxy/polyurethane semi-interpenetrating polymer networks for smart plaster

While numerous studies have explored the potential of shape memory materials in medical applications, the current research output is not enough for significant productivity in industrial products. In this research, a type of shape memory orthopedic plaster was fabricated by using epoxy/polyurethane interpenetrating networks modified with epoxidized soybean oil (ESO) and then compared with some commercial plasters. Polymer networks that were produced could be tailored to have glass transition temperatures (Tgs) within the range of 70–90 °C by changing the percentage composition of polyurethane and soybean oil. Shape recovery and fixity ratios in all samples were above 95 and 97 %. DMA results showed that IPNs with variable amount of soybean oil had lower glass transition temperature (Tg) and cross-link densities compared to IPNs without soybean oil. Based on the tensile test results, most samples exhibited an elastic modulus in the range of 280–400MPa, a level deemed somewhat acceptable when compared to commercial samples. Light microscope images had shown that the increase of polyurethane led to the phase separation of polymers, which was improved by the addition of soybean oil.

Versatile room temperature phosphorescence polymer with luminophore content as low as 0.05 wt%

To impart processability and practical serviceability to organic room temperature phosphorescence (RTP) molecules, and address phase separation and rigid confinement environment of conventional RTP polymers, a small amount of Schiff base bonds crosslinked tetraphenylene luminescence networks are pinned to the borate ester bonds crosslinked epoxy networks producing reversible interlocked polymer networks-based halogen-free RTP material. By taking advantage of the conjugation interaction of Schiff base linkages, and phase separation inhibition/molecular confinement effects of the interlocking networks, excellent fluorescence quantum yield (up to 78.9 %), RTP lifetime (660 ms) and quantum yield (16.7 %) are achieved with ultra-low concentration of luminophores (0.05 wt%). Moreover, the resultant acquires decent tensile strength (3.8 MPa) and a high elongation-at-break (365 %) owing to its unique molecular design. The phosphorescence lifetimes (457 ∼ 602 ms) are only slightly affected even after cyclic stretching (at 50 % strain for 100 cycles), or soaking in water (for 30 days), or heating (90 °C). The built-in reversible covalent bonds and the topological network reorganization further enable injection molding and self-healing of the material. Having been repeatedly crushed/hot-pressed, the recycled material still shows RTP lifetime and quantum yield of 398 ms and 14.6 %, respectively. The present work provides a feasible approach to fabricate multifunctional robust organic phosphorescent materials with application prospects.

Combining Functional Units to Design Organic Materials with Dynamic Room-Temperature Phosphorescence under Continuous Ultraviolet Irradiation.

Developing materials with dynamic room-temperature phosphorescence (RTP) properties is crucial for expanding the applications of organic light-emitting materials. In this study, we designed and synthesized two novel RTP molecules by combining functional units, incorporating the folded unit thianthrene into the classic luminescent cores thioxanthone or anthraquinone to construct TASO and TA2O. In this combination, the TA unit contributes to the enhancement of spin-orbit coupling (SOC), while the luminescent core governs the triplet energy level. After the strategic manipulation of SOC using the thianthrene unit, the target molecules exhibited a remarkable enhancement in RTP performance. This strategy led to the successful development of TASO and TA2O molecules with outstanding dynamic RTP properties when exposed to continuous ultraviolet irradiation, a result that can be ascribed to their efficient RTP, improved absorption ability, and oxygen-sensitive RTP properties. Leveraging the oxygen-mediated ultraviolet-radiation-induced RTP enhancement in TASO-doped polymer films, we developed a novel time-resolved detection technique for identifying phase separation in polymers with varying oxygen permeability. This research offers a promising approach for constructing materials with dynamic RTP properties.

A Flexible and Mechanical Robust All-Solid-State Polymer Electrolyte with Microphase Separated Structure for Lithium-Ion Battery.

Polyethylene oxide (PEO)-based electrolytes are the most widely used solid polymer electrolyte (SPE) due to their high safety, excellent ability to dissociate lithium salts, low cost, and ease of preparation. However, low ionic conductivity and narrow electrochemical stability window limit their potential for further development. "Polymer-in-salt" electrolytes exhibit superior electrochemical performance; however, the high lithium salt concentration makes the SPE mechanically fragile when facing lithium dendrites. Therefore, preparing an SPE that can withstand a high concentration of lithium salt while still maintaining good mechanical properties has become a valuable challenge. In this study, a macroscopically homogeneous but nanoscopically phase-separated polymer matrix was designed as an electrolyte that can withstand a high concentration of lithium salt while retaining good mechanical properties, and this study investigated changes in the Li+ solvation structure within the electrolyte and analyzed the reasons for the simultaneous achievement of good ionic conductivity (1.02 × 10-3 S cm-1 at 60 °C) and mechanical properties (7 MPa at room temperature). The formation of large ion clusters at the phase interface and selective enrichment of lithium salt in specific regions are found to play crucial roles, and the critical current density (CCD) can reach a value of 2.2 mA cm-2. This work demonstrates a promising design approach for polymer electrolytes that achieves an optimal balance between SPE conductivity and mechanical properties through microstructure control.

Porous Polymeric Nanofilms for Recreating the Basement Membrane in an Endothelial Barrier-on-Chip.

Organs-on-chips (OoCs) support an organotypic human cell culture in vitro. Precise representation of basement membranes (BMs) is critical for mimicking physiological functions of tissue interfaces. Artificial membranes in polyester (PES) and polycarbonate (PC) commonly used in in vitro models and OoCs do not replicate the characteristics of the natural BMs, such as submicrometric thickness, selective permeability, and elasticity. This study introduces porous poly(d,l-lactic acid) (PDLLA) nanofilms for replicating BMs in in vitro models and demonstrates their integration into microfluidic chips. Using roll-to-roll gravure coating and polymer phase separation, we fabricated transparent ∼200 nm thick PDLLA films. These nanofilms are 60 times thinner and 27 times more elastic than PES membranes and show uniformly distributed pores of controlled diameter (0.4 to 1.6 μm), which favor cell compartmentalization and exchange of large water-soluble molecules. Human umbilical vein endothelial cells (HUVECs) on PDLLA nanofilms stretched across microchannels exhibited 97% viability, enhanced adhesion, and a higher proliferation rate compared to their performance on PES membranes and glass substrates. After 5 days of culture, HUVECs formed a functional barrier on suspended PDLLA nanofilms, confirmed by a more than 10-fold increase in transendothelial electrical resistance and blocked 150 kDa dextran diffusion. When integrated between two microfluidic channels and exposed to physiological shear stress, despite their ultrathin thickness, PDLLA nanofilms upheld their integrity and efficiently maintained separation of the channels. The successful formation of an adherent endothelium and the coculture of HUVECs and human astrocytes on either side of the suspended nanofilm validate it as an artificial BM for OoCs. Its submicrometric thickness guarantees intimate contact, a key feature to mimic the blood-brain barrier and to study paracrine signaling between the two cell types. In summary, porous PDLLA nanofilms hold the potential for improving the accuracy and physiological relevance of the OoC as in vitro models and drug discovery tools.

New horizons on advanced nanoscale materials for Cultural Heritage conservation.

Nanomaterials have permeated numerous scientific and technological fields, and have gained growing importance over the past decades also in the preservation of Cultural Heritage. After a critical overview of the main nanomaterials adopted in art preservation, we provide new insights into some highly relevant gels, which constitute valuable tools to selectively remove dirt or other unwanted layers from the surface of works of art. In particular, the recent "twin-chain" gels, obtained by phase separation of two different PVAs and freeze-thawing, were considered as the most performing gel systems for the cleaning of Cultural Heritage. Three factors are crucial in determining the final gel properties, i.e., pore size, pore connectivity, and surface roughness, which belong to the micro/nanodomain. The pore size is affected by the molecular weight of the phase-separating PVA polymer, while pore connectivity and tortuosity likely depend on interconnections formed during gelation. Tortuosity greatly impacts on cleaning capability, as the removal of matter at the gel-target interface increases with the uploaded fluid's residence time at the interface (higher tortuosity produces longer residence). The gels' surface roughness, adaptability and stickiness can also be controlled by modulating the porogen amount or adding different polymers to PVA. Finally, PVA can be partially replaced with different biopolymers yielding gels with enhanced sustainability and effective cleaning capability, where the selection of the biopolymer affects the gel porosity and effectiveness. These results shed new light on the effect of micro/nanoscale features on the cleaning performances of "twin-chain" and composite gels, opening new horizons for advanced and "green"/sustainable gel materials that can impact on fields even beyond art preservation, like drug-delivery, detergency, food industry, cosmetics and tissue engineering.

Electrostatic-Dominated Conformational Fluctuations and Transition States of Phase Separation in Charge-Balanced Protein Polymer.

Hydration of the protein/polymer is the most important aspect of stability. It is well-known that salts alter the charged polymer's electrostatic forces, ultimately impacting its conformations in solution. The solvent effects lead to certain conformational fluctuations. Previous studies have shown the screening of electrostatic repulsion within the charge-imbalanced protein following charge inversion owing to counterion condensation and phase separation. This article studies conformation stability and phase separation of charge-balanced gelatin (a protein polymer at the isoelectric point) with the addition of different salts. A phenomenon has been reported where the electrostatic effect of salts results in conformational fluctuations in gelatin due to its insufficient hydrations (termed as starvation), which scales with salt concentration. This article also presents different transition states for charge-balanced proteins prior to phase separation. It is concluded that phase separation of a charge-balanced protein passes through a stable state followed by an unstable transition state, where certain unique interactions with salts occur.

Connecting Structural Characteristics and Material Properties in Phase-Separating Polymer Solutions: Phase-Field Modeling and Physics-Informed Neural Networks.

The formed morphology during phase separation is crucial for determining the properties of the resulting product, e.g., a functional membrane. However, an accurate morphology prediction is challenging due to the inherent complexity of molecular interactions. In this study, the phase separation of a two-dimensional model polymer solution is investigated. The spinodal decomposition during the formation of polymer-rich domains is described by the Cahn-Hilliard equation incorporating the Flory-Huggins free energy description between the polymer and solvent. We circumvent the heavy burden of precise morphology prediction through two aspects. First, we systematically analyze the degree of impact of the parameters (initial polymer volume fraction, polymer mobility, degree of polymerization, surface tension parameter, and Flory-Huggins interaction parameter) in a phase-separating system on morphological evolution characterized by geometrical fingerprints to determine the most influential factor. The sensitivity analysis provides an estimate for the error tolerance of each parameter in determining the transition time, the spinodal decomposition length, and the domain growth rate. Secondly, we devise a set of physics-informed neural networks (PINN) comprising two coupled feedforward neural networks to represent the phase-field equations and inversely discover the value of the embedded parameter for a given morphological evolution. Among the five parameters considered, the polymer-solvent affinity is key in determining the phase transition time and the growth law of the polymer-rich domains. We demonstrate that the unknown parameter can be accurately determined by renormalizing the PINN-predicted parameter by the change of characteristic domain size in time. Our results suggest that certain degrees of error are tolerable and do not significantly affect the morphology properties during the domain growth. Moreover, reliable inverse prediction of the unknown parameter can be pursued by merely two separate snapshots during morphological evolution. The latter largely reduces the computational load in the standard data-driven predictive methods, and the approach may prove beneficial to the inverse design for specific needs.

Chromatin compartmentalization regulates the response to DNA damage

The DNA damage response is essential to safeguard genome integrity. Although the contribution of chromatin in DNA repair has been investigated1,2, the contribution of chromosome folding to these processes remains unclear3. Here we report that, after the production of double-stranded breaks (DSBs) in mammalian cells, ATM drives the formation of a new chromatin compartment (D compartment) through the clustering of damaged topologically associating domains, decorated with γH2AX and 53BP1. This compartment forms by a mechanism that is consistent with polymer–polymer phase separation rather than liquid–liquid phase separation. The D compartment arises mostly in G1 phase, is independent of cohesin and is enhanced after pharmacological inhibition of DNA-dependent protein kinase (DNA-PK) or R-loop accumulation. Importantly, R-loop-enriched DNA-damage-responsive genes physically localize to the D compartment, and this contributes to their optimal activation, providing a function for DSB clustering in the DNA damage response. However, DSB-induced chromosome reorganization comes at the expense of an increased rate of translocations, also observed in cancer genomes. Overall, we characterize how DSB-induced compartmentalization orchestrates the DNA damage response and highlight the critical impact of chromosome architecture in genomic instability.

Thermodynamically controlled multiphase separation of heterogeneous liquid crystal colloids

Phase separation is a universal physical transition process whereby a homogeneous mixture splits into two distinct compartments that are driven by the component activity, elasticity, or compositions. In the current work, we develop a series of heterogeneous colloidal suspensions that exhibit both liquid-liquid phase separation of semiflexible binary polymers and liquid crystal phase separation of rigid, rod-like nanocellulose particles. The phase behavior of the multicomponent mixture is controlled by the trade-off between thermodynamics and kinetics during the two transition processes, displaying cholesteric self-assembly of nanocellulose within or across the compartmented aqueous phases. Upon thermodynamic control, two-, three-, and four-phase coexistence behaviors with rich liquid crystal stackings are realized. Among which, each relevant multiphase separation kinetics shows fundamentally different paths governed by nucleation and growth of polymer droplets and nanocellulose tactoids. Furthermore, a coupled multiphase transition can be realized by tuning the composition and the equilibrium temperature, which results in thermotropic behavior of polymers within a lyotropic liquid crystal matrix. Finally, upon drying, the multicomponent mixture undergoes a hierarchical self-assembly of nanocellulose and polymers into stratified cholesteric films, exhibiting compartmentalized polymer distribution and anisotropic microporous structure.

HP1-driven phase separation recapitulates the thermodynamics and kinetics of heterochromatin condensate formation

The spatial segregation of pericentromeric heterochromatin (PCH) into distinct, membrane-less nuclear compartments involves the binding of Heterochromatin Protein 1 (HP1) to H3K9me2/3-rich genomic regions. While HP1 exhibits liquid-liquid phase separation properties in vitro, its mechanistic impact on the structure and dynamics of PCH condensate formation in vivo remains largely unresolved. Here, using a minimal theoretical framework, we systematically investigate the mutual coupling between self-interacting HP1-like molecules and the chromatin polymer. We reveal that the specific affinity of HP1 for H3K9me2/3 loci facilitates coacervation in nucleo and promotes the formation of stable PCH condensates at HP1 levels far below the concentration required to observe phase separation in purified protein assays in vitro. These heterotypic HP1-chromatin interactions give rise to a strong dependence of the nucleoplasmic HP1 density on HP1-H3K9me2/3 stoichiometry, consistent with the thermodynamics of multicomponent phase separation. The dynamical cross talk between HP1 and the viscoelastic chromatin scaffold also leads to anomalously slow equilibration kinetics, which strongly depend on the genomic distribution of H3K9me2/3 domains and result in the coexistence of multiple long-lived, microphase-separated PCH compartments. The morphology of these complex coacervates is further found to be governed by the dynamic establishment of the underlying H3K9me2/3 landscape, which may drive their increasingly abnormal, aspherical shapes during cell development. These findings compare favorably to 4D microscopy measurements of HP1 condensate formation in live Drosophila embryos and suggest a general quantitative model of PCH formation based on the interplay between HP1-based phase separation and chromatin polymer mechanics.

Bioinspired Formation of Anti-Ultraviolet Micro-Goose Bump PDMAEMA/PS Coatings.

In this paper, inspired by the human-giving goosebumps process, we demonstrated a rapid, versatile, and simple method to prepare anti-UV microstructures polymer blend films with good morphology based on phase separation. Through the results of characterizations, it is proved that the microstructures are formed by polymer phase separation. Then the formation possibility of microstructures is proved by thermodynamic analysis. Moreover, the phase-field model is used to simulate the formation of microstructures by the finite element method, which can illustrate the evolution process of the microstructures. Besides, the microstructures were prepared on different substrates through the simple phase separation method, which can verify the versatility of this method. In addition, the anti-UV performance of the micro-structure films was evaluated. This work proposed a simple and versatile route to prepare microstructures coating in different substrates, which exhibit well anti-UV performance, and this work has the application potential for preventing material aging caused by UV radiation.

Conformational fluctuations and phases in fused in sarcoma (FUS) low-complexity domain.

The well-known phenomenon of phase separation in synthetic polymers and proteins has become a major topic in biophysics because it has been invoked as a mechanism of compartment formation in cells, without the need for membranes. Most of the coacervates (or condensates) are composed of Intrinsically Disordered Proteins (IDPs) or regions that are structureless, often in interaction with RNA and DNA. One of the more intriguing IDPs is the 526-residue RNA-binding protein, Fused in Sarcoma (FUS), whose monomer conformations and condensates exhibit unusual behavior that are sensitive to solution conditions. By focussing principally on the N-terminus low-complexity domain (FUS-LC comprising residues 1-214) and other truncations, we rationalize the findings of solid-state NMR experiments, which show that FUS-LC adopts a non-polymorphic fibril structure(core-1) involving residues 39-95, flanked by fuzzy coats on both the N- and C-terminal ends. An alternate structure (core-2), whose free energy is comparable to core-1, emerges only in the truncated construct (residues 110-214). Both core-1 and core-2 fibrils are stabilized by a Tyrosine ladder as well as hydrophilic interactions. The morphologies (gels, fibrils, and glass-like) adopted by FUS seem to vary greatly, depending on the experimental conditions. The effect of phosphorylation is site-specific. Simulations show that phosphorylation of residues within the fibril has a greater destabilization effect than residues that are outside the fibril region, which accords well with experiments. Many of the peculiarities associated with FUS may also be shared by other IDPs, such as TDP43 and hnRNPA2. We outline a number of problems for which there is no clear molecular explanation.

The efficient removal of low concentration hexavalent chromium via combining charged microporous membrane and micellar adsorption filtration

Abstract It is challenging to effectively purge wastewater containing heavy metal ions at low concentration. In order to remove trace Cr (VI) from wastewater efficiently, a positively charged microporous membrane was prepared by firstly non-solvent induced phase separation (NIPS) of amphiphilic polymer and secondly surface quaternization modification. The morphologies, surface roughness, surface charge, hydrophilicity, and pore size of membranes were characterized. Based on the dual action of micellar adsorption and charge repulsion, when surfactant is 4 mM and Cr (VI) is 60 ppm, the surface quaternization membrane (Q-MPVD) achieves 99.8 % Cr (VI) rejection simultaneously accompanied by a permeability of 100 LMH/bar. Meanwhile, the effects of STAC concentration, Cr (VI) concentration, pH as well as inorganic salt concentration on the composite micellar size, and Cr (VI) rejection performance were investigated, respectively. Moreover, the Q-MPVD membrane shows an excellent separation stability over a wide pH range, indicating its application perspective in engineering process. In summary, this work provided a positively charged membrane with high-efficiency performance for treating practical trace Cr (VI)-containing industrial wastewater.