Molecular cubic phases

The initial configuration is set up by building the field 0(r) for a unit cell first on a small cubic lattice, A = 3 or 5, analogously to a two-component, AB, molecular crystal. The value of the field 0(r) = at the point r = (f, 7, k)h on the lattice is set to 1 if, in the molecular crystal, an atom A is in this place if there is an atom B, 0, is set to —1 if there is an empty place, j is set to 0. Fig. 2 shows the initial configuration used to build the field 0(r) for the simple cubic-phase unit cell. Filled black circles represent atoms of type A and hollow circles represent atoms of type B. In this case all sites are occupied by atoms A or B. 

Brus and co-workers produced nanoparticles of CdSe from the pyrolysis of the single-molecular cadmium selenate precursor [Cd(SePh)2].392 The similar metal(benzylthiolate) compounds [M(SCH2C6i Is)2] (M = Zn, Cd) were also used in the solid-state preparation of ZnS and CdS particles and produced mixtures of the hexagonal and cubic phases of the crystallites, with sizes of 5nm, on thermolysis between 200 °C and 400 °C under nitrogen.393 The bis(trialkylsilyl)chalco-genides [(Me3SiE)2Cd] (E = S, Se), prepared by heterocumulene metathesis as in Equation (11), were used to produce nanoparticles. If the reactions are carried out in TOPO, TOPO-passivated CdE nanoparticles can be obtained although there was little control over particle size 394... 

The association of block copolymers in a selective solvent into micelles was the subject of the previous chapter. In this chapter, ordered phases in semidilute and concentrated block copolymer solutions, which often consist of ordered arrays of micelles, are considered. In a semidilute or concentrated block copolymer solution, as the concentration is increased, chains begin to overlap, and this can lead to the formation of a liquid crystalline phase such as a cubic phase of spherical micelles, a hexagonal phase of rod-like micelles or a lamellar phase. These ordered structures are associated with gel phases. Gels do not flow under their own weight, i.e. they have a finite yield stress. This contrasts with micellar solutions (sols) (discussed in Chapter 3) which flow readily due to a liquid-like organization of micelles. The ordered phases in block copolymer solutions are lyotropic liquid crystal phases that are analogous to those formed by low-molecular-weight surfactants. 

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)... 

The lipidic cubic phase has recently been demonstrated as a new system in which to crystallize membrane proteins [143, 144], and several examples [143, 145, 146] have been reported. The molecular mechanism for such crystallization is not yet clear, but the interfacial water and transport are believed to play an important role in nucleation and crystal growth [146, 147], Using a related model system of reverse micelles, drastic differences in water behavior were observed both experimentally [112, 127, 128, 133-135] and theoretically [117, 148, 149]. In contrast to the ultrafast motions of bulk water that occurs in less than several picoseconds, significantly slower water dynamics were observed in hundreds of picoseconds, which indicates a well-ordered water structure in these confinements. 

Intrinsic defects in molecular solids. Figure 4.14 shows the variations of r3 with T in succinonitrile [125, 129]. As sulfolan, this compound exhibits a brittle (monoclinic) phase up to 233 K, then a plastic body-centered cubic phase. The phase transition is well evidenced, with some hysteresis. However, above the phase transition point, x3 increases further in a sigmoidal way characteristic of defect formation. By using Eq. (24), the activation energy of the intrinsic molecular defect is obtained (0.36 eV). Analyzing the PALS spectra in four components confirms that x3 does represent the average between an o-Ps bulk lifetime, which decreases with T, and the constant lifetime of o-Ps trapped in the vacancies whose intensity increases with T. 

Application Qearly one important application of microporous materials in which the effectiveness is critically dependent on the monodispersity of the pores is the sieving of proteins. In order that an ultrafiltration membrane have high selectivity for proteins on the basis of size, the pore dimensions must first of all be on the order of 25 - ioOA, which is the size range provided by typical cubic phases. In addition to this, one important goal in the field of microporous matmals is the attainment of the narrowest possible pore size distribution, enabling isloation of proteins of a very specific molecular weight, for example. Applications in which separation of proteins by molecular weight are of proven or potential importance are immunoadsorption process, hemodialysis, purification of proteins, and microencapsulation of functionally-specific cells. 

It was clear that if the formulation O2+ [PtF,]- were true, then platinum hexafluoride should oxidize molecular oxygen. A sample of platinum hexafluoride was therefore prepared, and since it has a vapor pressure of 80 mm. at room temperature, the interaction with molecular oxygen was followed tensimetrically. The deep red (bromine colored) platinum hexafluoride vapor reacted instantly with the oxygen in a 1 1 molar ratio to give the familiar red compound. Interestingly, the solid made by this method at low temperatures, is iso-morphous and almost isodimensional with rhombohedral potassium hexafluoroplatinate (V). At higher temperatures transition to the cubic phase occurs. 

Surfactants are amphiphilic molecules which, when dispersed in a solvent, spontaneously self-assemble to form a wide variety of structures, including spherical and asymmetric micelles, hexagonal, lamellar, and a plethora of cubic phases. With the exception of the lamellar phase, each of these phase structures can exist in both normal and reverse orientations with the hydrophobic chains on the exterior of the aggregate, in contact with solvent or vice versa orientation. The range of structures a particular surfactant forms and the concentration range over which they form, depends upon the molecular architecture of the surfactant, its concentration, and the solvent in which it is dispersed. For example, some solvents such as ethanol do not support the formation of aggregates. As most pharmaceutical systems use water as their solvent, this entry will concentrate on aqueous-based systems, although other solvent systems, particularly other non-aqueous polar systems, will be mentioned where appropriate. 

Cubic phases are also unique in their ability to accommodate proteins as compared to other lipid-water phases. A wide range of globular proteins with molecular weights 5,000-150,000 are known to form cubic phases when mixed with lipids and water. So far few single ternary lipid-protein-water phase diagrams have been completely determined [7], [13] one system that has been looked at is that of monoolein-water-lysoz5one. Protein incorporation results in increased water swelling, and all three phases, Cp, Cd and CG/ occur. The protein molecules are located in the water channel systems and retain their native structure. This has been proved by thermal analysis of the phase, and measurements of enzymatic activity [7]. 

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