Adding crowding agents such as polyethylene glycol (PEG) to lyotropic chromonic liquid crystals (LCLCs) formed by water dispersions of materials such as disodium cromoglicate (DSCG) leads to a phase separation of the isotropic phase and the ordered phase. This behavior resembles nanoscale condensation of DNAs but occurs at the microscale. The structure of condensed chromonic regions in crowded dispersions is not yet fully understood, in particular, it is not clear whether the condensed domains are in the nematic (N) or the columnar (C) state. In this study, we report on small angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) measurements of mixtures of aqueous solutions of DSCG with PEG and compare results to measurements of aqueous solutions of pure DSCG. X-ray measurements demonstrate that addition of PEG to DSCG in the N phase triggers appearance of the C phase that coexists with the isotropic (I) phase. Within the coexisting region, the lateral distance between the columns of the chromonic aggregates decreases as the temperature is increased.
more »
« less
Interfacial tension and mechanism of liquid–liquid phase separation in aqueous media
The organization of multiple subcellular compartments is controlled by liquid–liquid phase separation. Phase separation of this type occurs with the emergence of interfacial tension. Aqueous two-phase systems formed by two non-ionic polymers can be used to separate and analyze biological macromolecules, cells and viruses. Phase separation in these systems may serve as the simple model of phase separation in cells also occurring in aqueous media. To better understand liquid–liquid phase separation mechanisms, interfacial tension was measured in aqueous two-phase systems formed by dextran and polyethylene glycol and by polyethylene glycol and sodium sulfate in the presence of different additives. Interfacial tension values depend on differences between the solvent properties of the coexisting phases, estimated experimentally by parameters representing dipole–dipole, ion–dipole, ion–ion, and hydrogen bonding interactions. Based on both current and literature data, we propose a mechanism for phase separation in aqueous two-phase systems. This mechanism is based on the fundamental role of intermolecular forces. Although it remains to be confirmed, it is possible that these may underlie all liquid–liquid phase separation processes in biology.
more »
« less
- Award ID(s):
- 1808281
- PAR ID:
- 10176370
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 22
- Issue:
- 8
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 4574 to 4580
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
more » « less
Proteinaceous liquid-liquid phase separation (LLPS) occurs when a polypeptide coalesces into a dense phase to form a liquid droplet (i.e., condensate) in aqueous solution. In vivo, functional protein-based condensates are often referred to as membraneless organelles (MLOs), which have roles in cellular processes ranging from stress responses to regulation of gene expression. Late embryogenesis abundant (LEA) proteins containing seed maturation protein domains (SMP; PF04927) have been linked to storage tolerance of orthodox seeds. The mechanism by which anhydrobiotic longevity is improved is unknown. Interestingly, the brine shrimp
Artemia franciscana is the only animal known to express such a protein (Afr LEA6) in its anhydrobiotic embryos. Ectopic expression ofAfr LEA6 (AWM11684) in insect cells improves their desiccation tolerance and a fraction of the protein is sequestered into MLOs, while aqueousAfr LEA6 raises the viscosity of the cytoplasm. LLPS ofAfr LEA6 is driven by the SMP domain, while the size of formed MLOs is regulated by a domain predicted to engage in protein binding.Afr LEA6 condensates formed in vitro selectively incorporate target proteins based on their surface charge, while cytoplasmic MLOs formed inAfr LEA6-transfected insect cells behave like stress granules. We suggest thatAfr LEA6 promotes desiccation tolerance by engaging in two distinct molecular mechanisms: by raising cytoplasmic viscosity at even modest levels of water loss to promote cell integrity during drying and by forming condensates that may act as protective compartments for desiccation-sensitive proteins. Identifying and understanding the molecular mechanisms that govern anhydrobiosis will lead to significant advancements in preserving biological samples. -
Nuclei of ordered materials emerging from the isotropic state usually show a shape topologically equivalent to a sphere; the well-known examples are crystals and nematic liquid crystal droplets. In this work, we explore experimentally and theoretically the toroidal in shape nuclei of columnar lyotropic chromonic liquid crystals coexisting with the isotropic phase. The geometry of these toroids depends strongly on concentrations of the disodium cromoglycate (DSCG) and the crowding agent, polyethylene glycol (PEG). High concentrations of DSCG and PEG result in thick toroids with small central holes, while low concentrations yield thin toroids with wide holes. The multitude of the observed shapes is explained by the balance of bending elasticity and anisotropic interfacial tension.more » « less
-
more » « less
Abstract Hydrophobic deep eutectic solvents (DESs) emerge as candidates to extract organic substrates from aqueous solutions. The DES‐aqueous liquid–liquid interface plays a vital role in the extraction ability of DESs because the nonbulk structure of interfacial molecules could cause thermodynamic and kinetic barriers. One question is how the DES compositions affect the structural features of the interface. We investigate the density profile, dipole moment, and hydrogen bonds of eight hydrophobic DES‐aqueous interfaces using molecular dynamics simulations. The eight DESs are composed of four organic compounds: decanoic acid, menthol, thymol, and lidocaine. The results show the variations of dipole moment and hydrogen bond structure and dynamics at the interfaces. These variations could influence the extraction ability of DES through adjusting the partition and kinetics of organic substrates in the DES‐aqueous biphasic systems. We also analyze the relationship between the variation of these interfacial features and the size and hydrophobicity of DES components.
-
more » « less
Herein, this progress report summarizes recent studies of electrochemical oxidation to modulate the interfacial tension of gallium‐based alloys. These liquid alloys have the largest interfacial tension of any liquid at room temperature. The ability to modulate the tension offers the possibility to create forces that change the shape and position of small volumes of liquid metal. It has been known since the late 1800s that electrocapillarity—the use of potential to modulate the electric double layer on the surface of metals in electrolyte—lowers the interfacial tension of liquid metals. This phenomenon, however, can only achieve modest changes in interfacial tension since it is limited to potentials that avoid Faradaic reactions. A recent discovery suggests reactions driven by the electrochemical oxidation of gallium alloys cause the interfacial tension to decrease from ≈500 mN m−1at 0 V to ≈0 mN m−1at less than 1 V. This change in interfacial tension is reversible, controllable, and goes well‐beyond what is possible via conventional electrocapillarity or surfactants. This report aims to introduce beginners to this field and address misconceptions. The report discusses applications that utilize modulations in interfacial tension of liquid metal and concludes with remaining opportunities and challenges needing further investigation.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c9cp05810a
