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At least 199 records · Page 11

Phase separated membrane bioreactor - Results from model system studies

The operation and evaluation of a bioreactor designed for high intensity oxygen transfer in a microgravity environment is described. The reactor itself consists of a zero headspace liquid phase separated from the air supply by a long length of silicone rubber tubing through which the oxygen diffuses in and the carbon dioxide diffuses out. Mass transfer studies show that the oxygen is film diffusion controlled both externally and internally to the tubing and not by diffusion across the tube walls. Methods of upgrading the design to eliminate these resistances are proposed. Cell growth was obtained in the fermenter using Saccharomyces cerevisiae showing that this concept is capable of sustaining cell growth in the terrestrial simulation.

Petersen, G. R.↗

Confinement-induced chirality in phase-separated achiral polymer solutions

Self-organization of polymers in constrained geometries largely determines their applications in high-strength materials, photonics, and electronics. Chiral organization under confinement is well established for polymers with intrinsic molecular chirality; however, it has not been observed for achiral polymers. Here, we report the emergence of chirality in spatially confined solutions of achiral rigid-rod polymers. We show that kinetically arrested phase separation of polymer solutions confined to narrow capillaries resulted in alternating segments of isotropic and chiral nematic phases. The chiral structure of the nematic segments originated from the interplay between the constrained geometry, surface anchoring, orientational wetting, and elastic anisotropy of rigid-rod polymers. The catenoidal shape of the chiral structure recapitulated the morphology of biological chiral structures. These findings provide insight into the organization of soft matter under spatial confinement and offer a straightforward way to form chiral structures from achiral synthetic polymers.

Science & Technology - Other Topics↗

Motility-induced phase separation and frustration in active matter swarmalators

Here we introduce a two dimensional system of active matter swarmalators composed of elastically interacting run-and-tumble active disks with an internal parameter Φ i . The disks experience an additional attractive or repulsive force with neighboring disks depending upon their relative difference in Φ i , making them similar to swarmalators used in robotic systems. In the absence of the internal parameter, the system forms a motility-induced phase separated (MIPS) state, but when the swarmalator interactions are present, a wide variety of other active phases appear depending upon whether the interaction is attractive or repulsive and whether the particles act to synchronize or ant-synchronize their internal parameter values. These phases include a gas-free gel regime, arrested clusters, a labyrinthine state, a regular MIPS state, a frustrated MIPS state for attractive antisynchronization, and a superlattice MIPS state for attractive synchronization.

97 MATHEMATICS AND COMPUTING↗

Additive Manufacturing of Poly(phenylene Sulfide) Aerogels via Simultaneous Material Extrusion and Thermally Induced Phase Separation

Abstract Additive manufacturing (AM) of aerogels increases the achievable geometric complexity, and affords fabrication of hierarchically porous structures. In this work, a custom heated material extrusion (MEX) device prints aerogels of poly(phenylene sulfide) (PPS), an engineering thermoplastic, via in situ thermally induced phase separation (TIPS). First, pre‐prepared solid gel inks are dissolved at high temperatures in the heated extruder barrel to form a homogeneous polymer solution. Solutions are then extruded onto a room‐temperature substrate, where printed roads maintain their bead shape and rapidly solidify via TIPS, thus enabling layer‐wise MEX AM. Printed gels are converted to aerogels via postprocessing solvent exchange and freeze‐drying. This work explores the effect of ink composition on printed aerogel morphology and thermomechanical properties. Scanning electron microscopy micrographs reveal complex hierarchical microstructures that are compositionally dependent. Printed aerogels demonstrate tailorable porosities (50.0–74.8%) and densities (0.345–0.684 g cm −3 ), which align well with cast aerogel analogs. Differential scanning calorimetry thermograms indicate printed aerogels are highly crystalline (≈43%), suggesting that printing does not inhibit the solidification process occurring during TIPS (polymer crystallization). Uniaxial compression testing reveals that compositionally dependent microstructure governs aerogel mechanical behavior, with compressive moduli ranging from 33.0 to 106.5 MPa.

Chemistry↗

The Thermodynamics of Crystallization and Phase-Separation in Melt-Derived Nuclear Waste Forms

This project aimed to gain detailed and fundamental understanding of the stability of glass waste forms to be used for safe and reliable encapsulation of nuclear waste. The focus was to understand thermodynamic and structural properties involved in crystallization and phase separation in melt-derived waste form glasses and glass-ceramics by studying a baseline glass composition with varying additives. This was achieved by combining neutron total scattering, advanced calorimetric measurements, and extensive modeling study. This project harnessed diverse and complementary approaches and expertise from four collaborating interdisciplinary institutions (two universities, one national laboratory, and one UK university partner). Samples were prepared at the national laboratory and exchanged with the two university institutions. The thermodynamic data obtained by various advanced calorimetry techniques were linked to the underlying short-range structure of waste forms measured by state-of-the-art neutron total scattering experiments. An important element of this project was extensive modeling to interpret and fundamentally understand the experimental results.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Phase separation, edge currents, and Hall effect for active matter with Magnus dynamics

Here we examine run-and-tumble disks in two-dimensional systems where the particles also have a Magnus component to their dynamics. For increased activity, we find that the system forms a motility-induced phase-separated (MIPS) state with chiral edge flow around the clusters, where the direction of the current is correlated with the sign of the Magnus term. The stability of the MIPS state is non-monotonic as a function of increasing Magnus term amplitude, with the MIPS region first extending down to lower activities followed by a break up of MIPS at large Magnus amplitudes into a gel-like state. We examine the dynamics in the presence of quenched disorder and a uniform drive and find that the bulk flow exhibits a drive-dependent Hall angle. This is a result of the side jump effect produced by scattering from the pinning sites and is similar to the behavior found for skyrmions in chiral magnets with quenched disorder.

97 MATHEMATICS AND COMPUTING↗

Simplified thermodynamic functions for vapor-liquid phase separation and fountain effect pumps

He-4 fluid handling devices near 2 K require novel components for non-Newtonian fluid transport in He II. Related sizing of devices has to be based on appropriate thermophysical property functions. The present paper presents simplified equilibrium state functions for porous media components which serve as vapor-liquid phase separators and fountain effect pumps.

Yuan, S. W. K.↗

Controllable protein phase separation and modular recruitment to form responsive membraneless organelles

Abstract Many intrinsically disordered proteins self-assemble into liquid droplets that function as membraneless organelles. Because of their biological importance and ability to colocalize molecules at high concentrations, these protein compartments represent a compelling target for bio-inspired materials engineering. Here we manipulated the intrinsically disordered, arginine/glycine-rich RGG domain from the P granule protein LAF-1 to generate synthetic membraneless organelles with controllable phase separation and cargo recruitment. First, we demonstrate enzymatically triggered droplet assembly and disassembly, whereby miscibility and RGG domain valency are tuned by protease activity. Second, we control droplet composition by selectively recruiting cargo molecules via protein interaction motifs. We then demonstrate protease-triggered controlled release of cargo. Droplet assembly and cargo recruitment are robust, occurring in cytoplasmic extracts and in living mammalian cells. This versatile system, which generates dynamic membraneless organelles with programmable phase behavior and composition, has important applications for compartmentalizing collections of proteins in engineered cells and protocells.

59 BASIC BIOLOGICAL SCIENCES↗

Facile preparation of porous nickel oxide membrane for flexible supercapacitors electrode via phase-separation method of polymer

Highlights: • Polymer/metal oxide hybrid membrane is fabricated for supercapacitors electrode. • Effects of membrane components on structure and performance are investigated. • The prepared electrode membrane shows high flexible property. • A capacitance of 794 F/g is obtained at a current density of 1.0 A/g. • Symmetric supercapacitor device exhibits an energy density of 39.6 Wh/kg. - Abstract: In this article, a porous flexible membrane electrode of nickel oxide is developed by a facile method based on liquid-liquid phase-separation. The effects of the membrane components on structures and electrochemical behaviors of membrane electrode are investigated. The results reveal that nano NiO and conducting graphite are imbedded into the polymer membrane of polyethersulfone to form a flexible hybrid membrane (M-NiO-G), which shows the highest specific capacitance of 794.0 F/g at a current density of 1.0 A/g. The asymmetrical supercapacitor device based on the as-synthesized of M-NiO-G (positive electrode) and activated carbon membrane (negative electrode) exhibits a high specific capacitance of 154.0 F/g at a current density of 0.2 A/g. The coulombic efficiency remains about 95.0%, and the capacitance retention is 84.8% after 5000 charging-discharging cycles at 1.0 A/g. The energy density of the asymmetrical supercapacitor device reaches 39.6 Wh/kg at a power density of 516.9 W/kg, still remains 20.0 Wh/kg at a high power density of 2567.4 W/kg in the potential window from 0 to 1.36 V in 6 M KOH aqueous solution.

36 MATERIALS SCIENCE↗

Amantadine interactions with phase separated lipid membranes

Amantadine, a small amphilphic organic compound that consists of an adamantane backbone and an amino group, was first recognized as an antiviral in 1963 and received approval for prophylaxis against the type A influenza virus in 1976. Since then, it has also been used to treat Parkinson’s disease-related dyskinesia and is being considered as a treatment for corona viruses. Since amantadine usually targets membrane-bound proteins, its interactions with the membrane are also thought to be important. Biological membranes are now widely understood to be laterally heterogeneous and certain proteins are known to preferentially co-localize within specific lipid domains. Does amantadine, therefore, preferentially localize in certain lipid composition domains? To address this question, here, we studied amantadine’s interactions with phase separating membranes composed of cholesterol, DSPC (1,2-distearoyl-sn-glycero-3-phosphocholine), POPC (1-palmitoyl-2-oleoyl-glycero-3-phosphocholine), and DOPC (1,2-dioleoyl-sn-glycero-3-phosphocholine), as well as single-phase DPhPC (1,2-diphytanoyl-sn-glycero-3-phos-phocholine) membranes. From Langmuir trough and differential scanning calorimetry (DSC) measurements, we determined, respectively, that amantadine preferentially binds to disordered lipids, such as POPC, and lowers the phase transition temperature of POPC/DSPC/cholesterol mixtures, implying that amantadine increases membrane disorder. Further, using droplet interface bilayers (DIBs), we observed that amantadine disrupts DPhPC membranes, consistent with its disordering properties. Finally, we carried out molecular dynamics (MD) simulations on POPC/DSPC/cholesterol membranes with varying amounts of amantadine. Consistent with experiment, MD simulations showed that amantadine prefers to associate with disordered POPC-rich domains, domain boundaries, and lipid glycerol backbones. Since different proteins co-localize with different lipid domains, our results have possible implications as to which classes of proteins may be better targets for amantadine.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hierarchical Membrane Dynamics in Phase-Separated Model Membranes

Lipid membranes, the primary matrix of cell membranes, exhibit a hierarchy of dynamics from molecular motions to collective undulations, which control spatiotemporal membrane phenomena and regulate various cellular functions. Thus, understanding how various dynamic modes influence membrane behavior is crucial to uncovering the design rules of cell membranes and implementing them in future technologies. Previous membrane dynamics studies using neutron spin-echo spectroscopy (NSE) have shed light on the dependence of collective membrane fluctuations on viscoelastic membrane properties, demonstrating that thickness fluctuation modes (100ns) are dictated by membrane viscosity, which directly governs fast (ps) molecular diffusive motions. Here, we focus on phase-separating lipid membranes, composed of DMPC:DSPC mixtures, to understand the effect of domain formation/growth on hierarchical matrix dynamics using selective lipid deuteration and different neutron spectroscopy techniques. NSE measurements on DMPC:DSPC-d83 (70:30 mol%) show that bending rigidity of the DMPC-rich matrix graduallyincreases with decreasing temperature - as the fully-fluid membrane approaches the upper phase transition (i.e. with the formation of transient DSPC clusters) - and increases further in the phase coexistence region with the growth of DSPC domains. Comparatively, NSE measurements on DMPC-d54:DSPC-d83 vesicles show pronounced matrix thickness fluctuations in the fully-fluid phase and drastic suppression of this fluctuation mode in the gel-fluid coexistence phase, even when the DMPC-rich matrix is still in its fluid phase. This suppression in fluctuations suggests an increase in the matrix viscosity with the growth of gel DSPC domains, which is further investigated by selectively measuring lipid diffusion in the DMPC-rich matrix using neutron backscattering spectroscopy. Comparisons of the experimental results with coarse-grained MD simulationsillustrate the underlying coupling mechanisms. Overall, these observations indicate a clear mechanical and viscoelastic coupling betweenlipid domains and their host matrix, suggesting that domain formation influences membrane properties beyond local effects.

Carrillo, Jan Michael↗

Directed Pore Uptake and Phase Separation of Surfactant Solutions under Confinement

The ability of a porous material to uptake and release molecules is determined by the thermodynamic state of preadsorbed surfactants in pore space. Yet, the effect of spatial confinement on the thermodynamic state of the surfactants is poorly understood. In this study, we use a combination of small-angle neutron scattering experiments and all-atom molecular dynamics simulations to develop a better understanding of the effect of confinement on self-assembly and temperature-induced liquid–liquid phase separation of surfactant solutions. Here, we study the demixing of a model nonionic surfactant triethyleneglycol monohexyl ether (C 6 E 3 ) in tubular nanopores of the SBA-15 silica material (pore diameter of 8.6 nm). We find that the nonionic surfactants display an enhanced in situ aggregation behavior in silica pores upon increasing the temperature above the lower critical solution temperature (LCST). The surfactant molecules directly bound to the pore walls act as anchor sites for subsequent adsorption, resulting in the increased uptake of nonanchored surfactants upon increasing temperature and driving an increase in the size of assemblies. The nonanchored surfactant molecules can be released into a bulk solvent by decreasing the temperature below LCST. This ability of C 6 E 3 surfactant allows reversible partitioning of secondary molecules (here dye) dissolved in the cores of surfactant micelles between the pore space and bulk solvent. The findings presented in the article provide fundamental insights into the surfactant assembly in confinement, which is crucial in the development of new multiresponsive materials for isolating and recovering molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nonmonotonic crossover in electronic phase separated manganite superlattices driven by the superlattice period

Studying manganite superlattices [(LCMO) 2n / (PCMO) n ] t made of La 0.625 Ca 0.375 MnO 3 (LCMO) and Pr 0.625 Ca 0.375 MnO 3 (PCMO), we found an unexpected behavior varying the period n. At small n, the ensemble is a three-dimensional ferromagnetic metal due to interfacial charge transfer. At large n , the LCMO layers dominate transport. However, rather than a smooth interpolation between these limits a sharp transport and magnetic anomaly is found at an intermediate critical PCMO thickness n*. Magnetic force microscopy reveals that the phase-separation length scale also maximizes at n* where, unexpectedly, it becomes comparable to that of the (La 1-y Pr y ) 0.625 Ca 0.375 MnO 3 (LPCMO) alloy. Finally, we conjecture the phenomenon originates in a disorder-related length scale: Large charge-ordered clusters as in LPCMO can only nucleate when Pr-rich regions reach a critical size related to n*.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Mesoscale Magnetostructural Phase Separation in Fe‐deficient Fe 5 GeTe 2

Two-dimensional van der Waals ferromagnet Fe 5-x GeTe 2 (F5GT) is promising for spintronic applications due to its high Curie temperature, layered structure, and ability to host complex magnetic textures. However, the origin of its sample-dependent magnetic anisotropy remains unclear, hindering control of its magnetic behavior. Here, we use spatially resolved cryogenic scanning transmission electron microscopy (STEM) to correlatively map magnetism, lattice structure, and chemistry across atomic-to-micron scales. We reveal that only mesoscale, not nanoscale, inclusions of a Fe-deficient secondary phase significantly modify magnetic behavior, establishing a previously unrecognized critical length scale. This phase separation, induced by quenching, leads to in-plane magnetic anisotropy, while slow cooling confines separation to a few nanometers and preserves out-of-plane anisotropy. These findings reconcile prior inconsistencies and establish a predictive framework for tuning magnetism in F5GT through thermal processing, with broader implications for controlling anisotropy in other two-dimensional magnetic materials.

2D ferromagnets↗

Foundry-compatible high-resolution patterning of vertically phase-separated semiconducting films for ultraflexible organic electronics

Solution processability of polymer semiconductors becomes an unfavorable factor during the fabrication of pixelated films since the underlying layer is vulnerable to subsequent solvent exposure. A foundry-compatible patterning process must meet requirements including high-throughput and high-resolution patternability, broad generality, ambient processability, environmentally benign solvents, and, minimal device performance degradation. However, known methodologies can only meet very few of these requirements. Here, a facile photolithographic approach is demonstrated for foundry-compatible high-resolution patterning of known p- and n-type semiconducting polymers. This process involves crosslinking a vertically phase-separated blend of the semiconducting polymer and a UV photocurable additive, and enables ambient processable photopatterning at resolutions as high as 0.5 μm in only three steps with environmentally benign solvents. The patterned semiconducting films can be integrated into thin-film transistors having excellent transport characteristics, low off-currents, and high thermal (up to 175 °C) and chemical (24 h immersion in chloroform) stability. Moreover, these patterned organic structures can also be integrated on 1.5 μm-thick parylene substrates to yield highly flexible (1 mm radius) and mechanically robust (5,000 bending cycles) thin-film transistors.

36 MATERIALS SCIENCE↗

ATP enhances at low concentrations but dissolves at high concentrations liquid-liquid phase separation (LLPS) of ALS/FTD-causing FUS

Highlights: • ATP is the energy currency but mysteriously with very high cellular concentrations. • ATP was recently decoded to dissolve LLPS of FUS whose aggregation leads to ALS. • Here we found for the first time that ATP can also enhance LLPS of FUS. • Therefore additional to being a hydrotrope, ATP also acts as a bivalent binder. • Our finding offers key clues in understanding age-dependent protein aggregation. ATP is the universal energy currency but mysteriously its cellular concentration is much higher than that needed for providing energy. Recently ATP was decoded to act as a hydrotrope to dissolve liquid-liquid phase separation (LLPS) of FUS whose aggregation leads to ALS/FTD. By DIC microscopy and NMR, here we characterized the effect of ATP on LLPS of FUS and its N-/C-terminal domains. Very unexpectedly, we found that like nucleic acids, ATP enhances LLPS of FUS at low but dissolves at high concentrations. Intriguingly, ATP monotonically dissolves LLPS of NTD, while it induces LLPS of CTD at low but dissolves at high concentrations. Our study reveals for the first time that ATP can enhance LLPS most likely by behaving as a bivalent binder. Most importantly, our results imply that age-dependent reduction of ATP concentrations may not only result in decreasing its capacity in preventing protein aggregation, but also in enhancing aggregation.

60 APPLIED LIFE SCIENCES↗

Phase Separation in (Ga,Mn)As Layers Obtained by Ion Implantation and Subsequent Laser Annealing

In this paper, we present the results of studies of the spectral, temperature, and field dependences of the transversal Kerr effect in Ga{sub 1 –} {sub x}Mn{sub x}As (x = 0.0066–0.033) layers produced by ion implantation and subsequent pulsed laser annealing. The complicated nonmonotonous nature of the temperature dependences of the transversal Kerr effect and its dependence on the measurement range indicate a magnetic inhomogeneity of the layers. The reasons for the inhomogeneity can be the Gaussian distribution of Mn over the thickness of the layers and the electron phase separation in them. The appearance of new features in the spectra of the transversal Kerr effect is explained by the presence in the doped semiconductor matrix of nanoregions with a higher carrier concentration and a higher Curie temperature and a shift of the Fermi level into the valence band leading to an increase in the energy of optical transitions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗