Water-in-water emulsion

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Water-in-water (W/W) emulsion is a system that consists of droplets of water-solvated molecules in another continuous aqueous solution; both the droplet and continuous phases contain different molecules that are entirely water-soluble. [1] As such, when two entirely aqueous solutions containing different water-soluble molecules are mixed, water droplets containing predominantly one component are dispersed in water solution containing another component. [2] Recently, such a water-in-water emulsion was demonstrated to exist and be stable from coalescence by the separation of different types of non-amphiphilic, but water-soluble molecular interactions. [3] These molecular interactions include hydrogen bonding, pi stacking, and salt bridging. This w/w emulsion was generated when the different water-solvated molecular functional groups get segregated in an aqueous mixture consisting of polymer and liquid crystal molecules.

Structure of disodium cromolyn glycate, DSCG Disodium cromolyn glycate.png
Structure of disodium cromolyn glycate, DSCG

This water-in-water emulsion consists of liquid crystals suspended as water-solvated droplets dispersed in a solution of polymer whose solvent is also water. The liquid crystal component of the emulsion is disodium cromolyn glycate (DSCG). This molecule is an anti-asthmatic drug, but also exists as a special type of liquid crystal when the concentration of DSCG is ~9-21 wt%. Unlike conventional lyotropic liquid crystals which consist of oily molecules such as 5CB, DSCG molecules are not amphiphilic, but entirely water-soluble. Thus, the separation of hydrophobic/hydrophilic groups cannot be applied to DSCG. The polymer solution serves as the medium or continuous phase of the w/w emulsion. Apart from being water-soluble, one important criterion for the generation of this w/w emulsion system is that the polymer cannot bear functional groups that interact strongly with DSCG. As such, ionic polymer when mixed with DSCG does not form w/w emulsion, but gives rise to a homogeneous solution or a precipitate solution. Consequently, the known polymers that afford w/w emulsion include polyacrylic amides and polyols. Surprisingly, some of these water-in-water emulsions can be exceptionally stable from coalescence for up to 30 days. Because molecules of liquid crystal assume a preferred common orientation among themselves, the overall orientation of liquid crystals in a droplet is only stable in certain configurations (Fig. 3). As water solvated droplets in a w/w emulsion, DSCG molecules would align in a preferred direction on the surface of the droplet. To minimize the overall energy of the system, the DSCG molecules in the droplet prefer to align either parallel or perpendicular to the surfaces of the droplets.(Fig. 4A,B).

Ww1c.png

The stability of this water-in-water emulsion from coalescence is attributed to three molecular forces:

1. The separation of different molecular forces at the beginning of the droplet formation. Similar forces tend to stay together: pi-stacking and salt bridging are the two dominant forces in the liquid crystal droplet phase, while hydrogen bonding governs in the continuous polymer phase.

Wwf4a.png
Wwf4b.png

2. As the droplet size increases, the molecular interactions at the interface of the droplet phase and the continuous phase become stronger through multivalent interactions. The strengthening of interfacial molecular interactions in w/w emulsions results in the formation of a layer of polymer that coats the surface of the droplet which consequently prevents droplets from clumping together.

3. In addition, it is also proposed that when two liquid crystal droplets merge (coalescence), the orientation of the liquid crystal molecules in the two merging droplets must change to “adapt” to each other, and thus incur an energy penalty which prevent the occurrence of coalescence.

This w/w emulsion also represents a new class of polymer dispersed liquid crystals(PDLC). Traditionally known PDLC consists of oil-in-water emulsion where the oily droplet is a thermotropic liquid crystal such as 4-pentyl-4'-cyanobiphenyl (5CB), and the water phase contains certain polymers. In comparison, this water-in-water emulsion consists of Polymer-Dispersed Lyotropic Liquid Crystals, where the lyotropic liquid crystal is DSCG molecules solvated in water. Traditional PDLCs have found application, from switchable windows to projection displays. The water-in-water emulsion of polymer-dispersed lyotropic liquid crystals has the potential for building highly bio-functional materials because of its compatibility with protein structure.

Other known types of water-in-water emulsions involve the separation of different biopolymers in aqueous solution.

Related Research Articles

<span class="mw-page-title-main">Colloid</span> Mixture of an insoluble substance microscopically dispersed throughout another substance

A colloid is a mixture in which one substance consisting of microscopically dispersed insoluble particles is suspended throughout another substance. Some definitions specify that the particles must be dispersed in a liquid, while others extend the definition to include substances like aerosols and gels. The term colloidal suspension refers unambiguously to the overall mixture. A colloid has a dispersed phase and a continuous phase. The dispersed phase particles have a diameter of approximately 1 nanometre to 1 micrometre.

An emulsion is a mixture of two or more liquids that are normally immiscible owing to liquid-liquid phase separation. Emulsions are part of a more general class of two-phase systems of matter called colloids. Although the terms colloid and emulsion are sometimes used interchangeably, emulsion should be used when both phases, dispersed and continuous, are liquids. In an emulsion, one liquid is dispersed in the other. Examples of emulsions include vinaigrettes, homogenized milk, liquid biomolecular condensates, and some cutting fluids for metal working.

<span class="mw-page-title-main">Liquid crystal</span> State of matter with properties of both conventional liquids and crystals

Liquid crystal (LC) is a state of matter whose properties are between those of conventional liquids and those of solid crystals. For example, a liquid crystal may flow like a liquid, but its molecules may be oriented in a crystal-like way. There are many types of LC phases, which can be distinguished by their optical properties. The contrasting textures arise due to molecules within one area of material ("domain") being oriented in the same direction but different areas having different orientations. LC materials may not always be in a LC state of matter.

<span class="mw-page-title-main">Solution (chemistry)</span> Homogeneous mixture of a solute and a solvent

In chemistry, a solution is a special type of homogeneous mixture composed of two or more substances. In such a mixture, a solute is a substance dissolved in another substance, known as a solvent. If the attractive forces between the solvent and solute particles are greater than the attractive forces holding the solute particles together, the solvent particles pull the solute particles apart and surround them. These surrounded solute particles then move away from the solid solute and out into the solution. The mixing process of a solution happens at a scale where the effects of chemical polarity are involved, resulting in interactions that are specific to solvation. The solution usually has the state of the solvent when the solvent is the larger fraction of the mixture, as is commonly the case. One important parameter of a solution is the concentration, which is a measure of the amount of solute in a given amount of solution or solvent. The term "aqueous solution" is used when one of the solvents is water.

Emulsion polymerization is a type of radical polymerization that usually starts with an emulsion incorporating water, monomer, and surfactant. The most common type of emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer are emulsified in a continuous phase of water. Water-soluble polymers, such as certain polyvinyl alcohols or hydroxyethyl celluloses, can also be used to act as emulsifiers/stabilizers. The name "emulsion polymerization" is a misnomer that arises from a historical misconception. Rather than occurring in emulsion droplets, polymerization takes place in the latex/colloid particles that form spontaneously in the first few minutes of the process. These latex particles are typically 100 nm in size, and are made of many individual polymer chains. The particles are prevented from coagulating with each other because each particle is surrounded by the surfactant ('soap'); the charge on the surfactant repels other particles electrostatically. When water-soluble polymers are used as stabilizers instead of soap, the repulsion between particles arises because these water-soluble polymers form a 'hairy layer' around a particle that repels other particles, because pushing particles together would involve compressing these chains.

<span class="mw-page-title-main">Micelle</span> Group of fatty molecules suspended in liquid by soaps and/or detergents

A micelle or micella is an aggregate of surfactant amphipathic lipid molecules dispersed in a liquid, forming a colloidal suspension. A typical micelle in water forms an aggregate with the hydrophilic "head" regions in contact with surrounding solvent, sequestering the hydrophobic single-tail regions in the micelle centre.

<span class="mw-page-title-main">Flocculation</span> Process by which colloidal particles come out of suspension to precipitate as floc or flake

In colloidal chemistry, flocculation is a process by which colloidal particles come out of suspension to sediment in the form of floc or flake, either spontaneously or due to the addition of a clarifying agent. The action differs from precipitation in that, prior to flocculation, colloids are merely suspended, under the form of a stable dispersion and are not truly dissolved in solution.

Liquid–liquid extraction (LLE), also known as solvent extraction and partitioning, is a method to separate compounds or metal complexes, based on their relative solubilities in two different immiscible liquids, usually water (polar) and an organic solvent (non-polar). There is a net transfer of one or more species from one liquid into another liquid phase, generally from aqueous to organic. The transfer is driven by chemical potential, i.e. once the transfer is complete, the overall system of chemical components that make up the solutes and the solvents are in a more stable configuration. The solvent that is enriched in solute(s) is called extract. The feed solution that is depleted in solute(s) is called the raffinate. LLE is a basic technique in chemical laboratories, where it is performed using a variety of apparatus, from separatory funnels to countercurrent distribution equipment called as mixer settlers. This type of process is commonly performed after a chemical reaction as part of the work-up, often including an acidic work-up.

Microemulsions are clear, thermodynamically stable isotropic liquid mixtures of oil, water and surfactant, frequently in combination with a cosurfactant. The aqueous phase may contain salt(s) and/or other ingredients, and the "oil" may actually be a complex mixture of different hydrocarbons. In contrast to ordinary emulsions, microemulsions form upon simple mixing of the components and do not require the high shear conditions generally used in the formation of ordinary emulsions. The three basic types of microemulsions are direct, reversed and bicontinuous.

Aqueous biphasic systems (ABS) or aqueous two-phase systems (ATPS) are clean alternatives for traditional organic-water solvent extraction systems.

<span class="mw-page-title-main">Ostwald ripening</span> Process by which small crystals dissolve in solution for the benefit of larger crystals

Ostwald ripening is a phenomenon observed in solid solutions or liquid sols that describes the change of an inhomogeneous structure over time, i.e., small crystals or sol particles dissolve, and redeposit onto larger crystals or sol particles.

<span class="mw-page-title-main">Coacervate</span>

Coacervate is an aqueous phase rich in macromolecules such as synthetic polymers, proteins or nucleic acids. It forms through liquid-liquid phase separation (LLPS), leading to a dense phase in thermodynamic equilibrium with a dilute phase. The dispersed droplets of dense phase are also called coacervates, micro-coacervates or coacervate droplets. These structures draw a lot of interest because they form spontaneously from aqueous mixtures and provide stable compartmentalization without the need of a membrane.

A dispersion is a system in which distributed particles of one material are dispersed in a continuous phase of another material. The two phases may be in the same or different states of matter.

<span class="mw-page-title-main">Lyotropic liquid crystal</span>

Lyotropic liquid crystals result when fat-loving and water-loving chemical compounds known as amphiphiles dissolve into a solution that behaves both like a liquid and a solid crystal. This liquid crystalline mesophase includes everyday mixtures like soap and water.

A Ramsden emulsion, sometimes named Pickering emulsion, is an emulsion that is stabilized by solid particles which adsorb onto the interface between the water and oil phases. Typically, the emulsions are either water-in-oil or oil-in-water emulsions, but other more complex systems such as water-in-water, oil-in-oil, water-in-oil-in-water, and oil-in-water-in-oil also do exist. Pickering emulsions were named after S.U. Pickering, who described the phenomenon in 1907, although the effect was first recognized by Walter Ramsden in 1903.

<span class="mw-page-title-main">Janus particles</span> Type of nanoparticle or microparticle

Janus particles are special types of nanoparticles or microparticles whose surfaces have two or more distinct physical properties. This unique surface of Janus particles allows two different types of chemistry to occur on the same particle. The simplest case of a Janus particle is achieved by dividing the particle into two distinct parts, each of them either made of a different material, or bearing different functional groups. For example, a Janus particle may have one-half of its surface composed of hydrophilic groups and the other half hydrophobic groups, the particles might have two surfaces of different color, fluorescence, or magnetic properties. This gives these particles unique properties related to their asymmetric structure and/or functionalization.

<span class="mw-page-title-main">Temperature-responsive polymer</span> Polymer showing drastic changes in physical properties with temperature

Temperature-responsive polymers or thermoresponsive polymers are polymers that exhibit drastic and discontinuous changes in their physical properties with temperature. The term is commonly used when the property concerned is solubility in a given solvent, but it may also be used when other properties are affected. Thermoresponsive polymers belong to the class of stimuli-responsive materials, in contrast to temperature-sensitive materials, which change their properties continuously with environmental conditions. In a stricter sense, thermoresponsive polymers display a miscibility gap in their temperature-composition diagram. Depending on whether the miscibility gap is found at high or low temperatures, either an upper critical solution temperature (UCST) or a lower critical solution temperature (LCST) exists.

<span class="mw-page-title-main">Emulsion dispersion</span>

An emulsion dispersion is thermoplastics or elastomers suspended in a liquid state by means of emulsifiers.

Paint has four major components: pigments, binders, solvents, and additives. Pigments serve to give paint its color, texture, toughness, as well as determining if a paint is opaque or not. Common white pigments include titanium dioxide and zinc oxide. Binders are the film forming component of a paint as it dries and affects the durability, gloss, and flexibility of the coating. Polyurethanes, polyesters, and acrylics are all examples of common binders. The solvent is the medium in which all other components of the paint are dissolved and evaporates away as the paint dries and cures. The solvent also modifies the curing rate and viscosity of the paint in its liquid state. There are two types of paint: solvent-borne and water-borne paints. Solvent-borne paints use organic solvents as the primary vehicle carrying the solid components in a paint formulation, whereas water-borne paints use water as the continuous medium. The additives that are incorporated into paints are a wide range of things which impart important effects on the properties of the paint and the final coating. Common paint additives are catalysts, thickeners, stabilizers, emulsifiers, texturizers, biocides to fight bacterial growth, etc.

Macroemulsions are dispersed liquid-liquid, thermodynamically unstable systems with particle sizes ranging from 1 to 100 μm, which, most often, do not form spontaneously. Macroemulsions scatter light effectively and therefore appear milky, because their droplets are greater than a wavelength of light. They are part of a larger family of emulsions along with miniemulsions. As with all emulsions, one phase serves as the dispersing agent. It is often called the continuous or outer phase. The remaining phase(s) are disperse or inner phase(s), because the liquid droplets are finely distributed amongst the larger continuous phase droplets. This type of emulsion is thermodynamically unstable, but can be stabilized for a period of time with applications of kinetic energy. Surfactants are used to reduce the interfacial tension between the two phases, and induce macroemulsion stability for a useful amount of time. Emulsions can be stabilized otherwise with polymers, solid particles or proteins.

References

  1. B. T. Nguyen; T. Nicolai & L. Benyahia (2013). "Stabilization of Water-in-Water Emulsions by Addition of Protein Particles". Langmuir. 23 (3): 1453–1458. doi:10.1021/la402131e. PMID   23895275.
  2. I. Capron; S. Costeux & M. Djabourov (2001). "Water in Water Emulsions: Phase Separation and Rheology of Biopolymer Solutions". Rheologica Acta. 40 (5): 441–456. doi:10.1007/s003970100161.
  3. K. A. Simon; P. Sejwal; R. B. Gerecht & Y.-Y. Luk (2007). "Water-in-Water Emulsions Stabilized by Non-Amphiphilic Interactions: Polymer-Dispersed Lyotropic Liquid Crystals". Langmuir. 40 (5): 441–456. doi:10.1021/la062203s.

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1. Salt bridging and example of salt bridges http://www.cryst.bbk.ac.uk/PPS2/projects/day/TDayDiss/SaltBridges.html

2. Tutorial on liquid crystals http://outreach.lci.kent.edu/

3. Introduction to polymer dispersed liquid crystals (PDLC)

4. Droplet configuration of PDLC’s http://plc.cwru.edu/tutorial/enhanced/files/pdlc/droplet/droplet.htm