Cubic phase bicontinuous

These phases can be several different structures, where the surfactant molecules form aggregates that penetrate space, forming a porous connected structure in 

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In the latter the surfactant monolayer (in oil and water mixture) or bilayer (in water only) forms a periodic surface. A periodic surface is one that repeats itself under a unit translation in one, two, or three coordinate directions similarly to the periodic arrangement of atoms in regular crystals. It is still not clear, however, whether the transition between the bicontinuous microemulsion and the ordered bicontinuous cubic phases occurs in nature. When the volume fractions of oil and water are equal, one finds the cubic phases in a narrow window of surfactant concentration around 0.5 weight fraction. However, it is not known whether these phases are bicontinuous. No experimental evidence has been published that there exist bicontinuous cubic phases with the ordered surfactant monolayer, rather than bilayer, forming the periodic surface. 

Figure 2a shows a schematic phase diagram for lyotropic liquid crystals. This figure shows the formation of micelles, cubic phases, bicontinuous cubic phases, and lamellar phases as the concentration of surfactant increases. Also shown in this figure is a schematic diagram of an ordered bicontinuous cubic phase (Fig. 2b). Another interesting example in...

In the Hn phase and in the inverted micellar cubic phase, the water associated with the polar headgroups is trapped inside a ring structure and is not in rapid exchange with bulk water [18]. In a bicontinuous cubic phase, however, there is a continuous network of aqueous channels. 

It is believed that the Gaussian bending modulus k controls the membrane topology. In particular, a negative value of this constant is needed for stable bilayers. A positive value will induce nonlamellar topologies, such as bicontinuous cubic phases. Therefore, it is believed that k is negative for membranes. 

Bicontinuous cubic phase Lamellar phase Bicontinuous cubic phase Reverse hexagonal columnar phase Inverse cubic phase (inverse micellar phase)... 

Cyclic carbohydrates with two alkyl chains (e.g. 1,2-dialkyl (or 1,2-diacyl) glycerol 8 a (sug=Glcp, Galp) present structural similarities with glycerophospho-lipids. They form complex mesophases such as bicontinuous cubic phases, inverted hexagonal phases or myelin figures [58-61]. Other dialkyl derivatives... 

Figure 9.18 Idealized structures of hydrated didodecyl-phosphatidyl ethanolamine showing some typical bicontinuous cubic phases. (Adapted from Seddon et al, 1990 see this reference for the indicated crystallographic nomenclature.)...

Bicontinuous cubic phases have not, to date, been accounted for using SSL theory. The OBDD phase has been shown to be unstable with respect to lam and hex phases (Likhtman and Semenov 1994 Olmsted and Milner 1994a,b). As discussed above, it now appears that the OBDD was a misidentified gyroid phase however, SSL calculations for the gyroid structure have not been performed as yet. A perforated layer structure was found to be unstable by Fredrickson (1991), using SSL theory following Semenov s method. 

Cr Cub, Cubv d E G HT Iso Isore l LamN LaniSm/col Lamsm/dis LC LT M N/N Rp Rh Rsi SmA Crystalline solid Spheroidic (micellar) cubic phase Bicontinuous cubic phase Layer periodicity Crystalline E phase Glassy state High temperature phase Isotropic liquid Re-entrant isotropic phase Molecular length Laminated nematic phase Correlated laminated smectic phase Non-correlated laminated smectic phase Liquid crystal/Liquid crystalline Low temperature phase Unknown mesophase Nematic phase/Chiral nematic Phase Perfluoroalkyl chain Alkyl chain Carbosilane chain Smectic A phase (nontilted smectic phase)... 

Due to the rigidity of Rp-chains, in fluorinated LCs the transition from smectic to columnar organization often takes place via modulated smectic phases (ribbon phases, c2mm, p2gg, and Colob see Fig. 20, left) which completely or partly replace the bicontinuous cubic phases at the Sm-to-Col cross-over. Similarly, in columnar phases the circular columns can be deformed to an elliptic, rectangular, or square... 

An example of a special kind of mesogenic compound is provided by A,A -bis (4-alkoxybenzoylhydrazines) (e.g., compound 132a,) known to form bicontinuous cubic phases [247-249]. It is interesting that fluorination of only one chain of these compounds (compound 132b) removes the cubic phase which is restored if the second alkyl chain is also fluorinated (compound 132c, see Fig. 35a) [122]. 

This behavior of the DPoPE/cationic PC mixtures is not surprising, because both the double bonds and hydrocarbon chain length variations are known to have considerable effect on the lamellar-to-nonlamellar transitions in lipids [113]. A specific structural characteristic of lipid arrays that exhibits distinct change around the chain length of 14 carbons is the formation of inverted bicontinuous cubic phases Qn. The latter phases tend to form in diacyl or dialkyl phospholipids... 

Templer RH, Seddon JM, Duesing PM et al (1998) Modeling the phase behavior of the inverse hexagonal and inverse bicontinuous cubic phases in 2 1 fatty acid phosphatidylcholine mixtures. J Phys Chem B 102 7262-7271... 

For diblock copolymers, periodically arranged spheres (micelles), hexago-nally packed cylinders, and a lamellar phase have been observed [1]. A more complex bicontinuous cubic phase with QIasymmetry (gyroid structure) has also been identified. These supramolecular structures, with length scales on the order of 1 to 102 nm, may be controlled by changing the amount of solvent, the length of blocks, or the proportions of A and B monomeric units [128-131]. 

FIGURE 4.2 Schematic illustration of 2 x 2 x 2 unit cells of a lipid/water phase with gyroid cubic symmetry. In reversed bicontinuous cubic phases the lipid bilayer membrane separates two intertwined water-filled subvolumes resembling 3D arrays of interconnected tunnels. Black box (right) represents an enlargement of a part of the folded liquid crystalline lipid bilayer membrane structure. 

Engblom, J. The bicontinuous cubic phase—A model for investigating the effects on a lipid bilayer due to a foreign substance illustrated by the skin penetration enhancer Azone. Chemistry and Physics of Lipids S4(2) 155-164, 1996. 

The polymerization of one or more components of a lyotropic liquid crys in such a way as to preserve and fixate the microstructure has recently been successfully performed. This opens up new avenues for the study and technological application of these periodic microstructures. Of particular importance are the so-called bicontinuous cubic phases, having triply-periodic microstructures in which aqueous and hydrocarbon components are simultaneously continuous. It is shown that the polymerization of one of these components, followed by removal of the liquid components, leads to the first microporous polymeric material exhibiting a continuous, triply-periodic porespace with monodisperse, nanometer-sized pores. It is also shown that proteins can be immobilized inside of polymmzed cubic phases to create a reaction medium allowing continuous flow of reactants and products, and providing a natural lipid environment for the proteins. 

This chapter focuses on the fixation of lyotropic liquid crystalline phases by the polymerization of one (or more) component(s) following equilibration of the phase. The primary emphasis will be on the polymerization of bicontinuous cubic phases, a particular class of liquid crystals which exhibit simultaneous continuity of hydrophilic — usually aqueous — and hydrophobic — typically hydrocarbon — components, a property known as bicontinuity (1), together with cubic crystallographic symmetry (2). The potential technological impact of such a process lies in the fact that after polymerization of one component to form a continuous polymeric matrix, removal of the other component creates a microporous material with a highly-branched, monodisperse, triply-periodic porespace (3). 

While there have been efforts to polymerize other surfactant mesophases and metastable phases, bicontinuous cubic phases have only very recently been the subject of polymerization work. Through the use of polymerizable surfactants, and aqueous monomers, in particular acrylamide, polymerization reactions have been performed in vesicles (4-8). surfactant foams ), inverted micellar solutions (10). hexagonal phase liquid crystals (111, and bicontinuous microemulsions (121. In the latter two cases rearrangement of the microstructure occured during polymerization, which in the case of bicontinuous microemulsions seems inevitable b ause microemulsions are of low viscosity and continually rearranging on the timescale of microseconds due to thermal disruption (131. In contrast, bicontinuous cubic phases are extremely viscous in genei, and although the components display self-diffusion rates comparable to those... 

The Known Bicontinuous Cubic Phase Structures. Recording the structures that have been proposed for bicontinuous cubic phases ... 

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