Hydrophobic organic liquids

We will describe two mesoscale, self-assembling systems in which the interactions between objects are based on capillary forces. The first is based on polyhedral polydimethylsiloxane (PDMS) objects at a perfluorodecalin (PFD)/H20 interface. These objects have their faces patterned to be either hydrophobic or hydrophilic, and they assemble via lateral capillary forces that originate from interactions between these faces (Fig. 4. la). The second system uses polyhedral objects that are suspended in water and have selected faces covered with a water-insoluble liquid - either a hydrophobic organic liquid or a liquid metal solder these objects assemble via capillary forces into three-dimensional (3D) structures (Fig. 4.1b). 

Generally, a continuous phase that is a nonsolvent for the microencapsulated bioactive compound is favorable. For lipophilic compounds, aqueous solutions may be comfortably chosen while the use of hydrophobic, organic liquids is preferred as coutinuous phase for the encapsulation of hydrophilic compounds. The ideal rate of solvent removal depends on a variety of factors like the type of matrix material, drug and solvent as weU as the desired release profile of the microspheres. 

Ghoshal S, RG Luthy (1996) Bioavailability of hydrophobic organic compounds from nonaqueous-phase liquids the biodegradation of naphthalene from coal tar. Environ Toxicol Chem 15 1894-1900. 

In earlier work, Bhaumik and Kumar (1995) have reported that the use of two liquid phases in the oxidation of hydrophobic organic substances with aqueous H2O2 using titanium silicate as the catalyst not only enhances the rate of oxidation but also improves selectivity for species like toluene, anisole, and benzyl alcohol. For a single liquid phase acetonitrile was u.sed a solvent. The solid-liquid system gives high ortho selectivity. Thus, in the case of anisole the ratios of o to p for. solid-liquid and solid-liquid-liquid system were 2.22 1 and 0.35 1, respectively. 

Adrian et al. (2000) have reported a novel high-pressure liquid-liquid extraction process with reference to processing in biotechnology the example of cardiac glycosides (digitoxin and digoxin) is cited. A completely miscible, binary system of water and a hydrophobic organic solvent like ethanol can split into two liquid phases when a near-critical gas (e.g. CO2) is added. The near-critical C02/water/l-propanol system is reported, for which possibilities for industrial exploitation exist. 

The rheological properties of a fluid interface may be characterized by four parameters surface shear viscosity and elasticity, and surface dilational viscosity and elasticity. When polymer monolayers are present at such interfaces, viscoelastic behavior has been observed (1,2), but theoretical progress has been slow. The adsorption of amphiphilic polymers at the interface in liquid emulsions stabilizes the particles mainly through osmotic pressure developed upon close approach. This has become known as steric stabilization (3,4.5). In this paper, the dynamic behavior of amphiphilic, hydrophobically modified hydroxyethyl celluloses (HM-HEC), was studied. In previous studies HM-HEC s were found to greatly reduce liquid/liquid interfacial tensions even at very low polymer concentrations, and were extremely effective emulsifiers for organic liquids in water (6). 

Microbes were frequently found to synthesise surface-active molecules in order to mobilise hydrophobic organic substrates. These biosurfactants, which are either excreted by the producing organisms or remain bound to their cell surfaces, are composed of a hydrophilic part making them soluble in water and a lipophilic part making them accumulate at interfaces. With respect to their physical effects, one can distinguish two types of biosurfactants firstly, molecules that drastically reduce the surface and interfacial tensions of gas-liquid, liquid-liquid and liquid-solid systems, and, secondly, compounds that stabilise emulsions of nonaqueous phase liquids in water, often also referred to as bioemulsifiers. The former molecules are typically low-molar-mass... 

At concentrations above their aqueous solubility, the so-called c.m.c., low-molar-mass biosurfactants form micelles in the aqueous phase. Micelles are spherical or lamellar aggregates with a hydrophobic core and a hydrophilic outer surface. They are capable of solubilising nonpolar chemicals in their hydrophobic interior, and can thereby mobilise separate phase (liquid, solid or sorbed) hydrophobic organic compounds. The characteristics for the efficiency of (bio)surfactants are the extent of the reduction of the surface or interfacial tension, the c.m.c. as a measure of the concentration needed to bring about this reduction, and the molar solubilisation ratio MSR, which is the number of moles of a chemical solubilised per mole of surfactant in the form of micelles [96]. 

The ethylene oxide block is hydrophilic, whereas the propylene oxide block is (relatively) hydrophobic. The copolymer forms micelles in aqueous solutions with the hydrophilic portions pointing outward, interacting with the water, while the hydrophobic portions form the inner core, shielded from the water by the ethylene oxide-derived block. A micelle is also formed in organic liquids, but here the hydrophobic propylene oxide block faces outward, whereas the ethylene oxide bloek acts as the inner eore. 

As a strong polar proton donor, water is strongly absorbed in most ionic liquids. In the extreme case, it is fully miscible with ionic liquids, such as [BMIM]Bp4 and [BMIMJCFsCOj. Even the hydrophobic ionic liquids can pick up a low concentration of water, resulting in a reduced absorption affinity for some organic compounds (27). The presence of water may, therefore, influence the performance of an ionic liquid in catalytic applications. 

BMIM]BF4 was applied to a Suzuki reaction. The active catalyst was a trico-ordinated [Pd(PPh3)2(Ar)][X] complex that formed after oxidative addition of aryl halide to [Pd(0)(PPh3)4] 211). The hydrophobic ionic liquid does not compete with the unsaturated organic substrate for the electrophilic active metal center. 

Ionic liquids are a class of solvents and they are the subject of keen research interest in chemistry (Freemantle, 1998). Hydrophobic ionic liquids with low melting points (from -30°C to ambient temperature) have been synthesized and investigated, based on 1,3-dialkyl imidazolium cations and hydrophobic anions. Other imidazolium molten salts with hydrophilic anions and thus water-soluble are also of interest. NMR and elemental analysis have characterized the molten salts. Their density, melting point, viscosity, conductivity, refractive index, electrochemical window, thermal stability, and miscibility with water and organic solvents were determined. The influence of the alkyl substituents in 1,2, 3, and 4(5)-positions on the imidazolium cation on these properties has been scrutinized. Viscosities as low as 35 cP (for l-ethyl-3-methylimi-dazolium bis((trifluoromethyl)sulfonyl)amide (bis(triflyl)amide) and trifluoroacetate) and conductivities as high as 9.6 mS/cm were obtained. Photophysical probe studies were carried out to establish more precisely the solvent properties of l-ethyl-3-methyl-imidazolium bis((trifluoromethyl)sulfonyl)amide. The hydrophobic molten salts are promising solvents for electrochemical, photovoltaic, and synthetic applications (Bon-hote et al., 1996). 

C. The Interaction of Hydrophobic Solids with Organic Liquids. 283... 

A (macro (emulsion is formed when two immiscible liquids, usually water and a hydrophobic organic solvent, an oil. are mechanically agitated so that one liquid forms droplets in the other one. A microemulsion, on the other hand, forms spontaneously because of the self-association of added amphiphilic molecules. During the emulsification agitation both liquids form droplets, and with no stabilization, two emulsion layers are formed, one with oil droplets in water fo/w) and one of water in oil (w/o). However, if not stabilized the droplets separate into two phases when the agitaliun ceases. If an emulsifier (a stabilizing compound) is added to the two immiscible liquids, one of them becomes continuous and the other one remains in droplet form. 

Most of these aspects of water-sorption equilibrium correspond to the equality of chemical potentials of water in the medium and in the polymer. The consequences of this principle are illustrated by the experiment of Fig. 14.2, where an interface is created between water and a nonmiscible liquid (oil, hydrocarbon, etc.), and a polymer sample is immersed into the organic liquid. It can be observed that, despite the hydrophobic character of the surrounding medium, the sample reaches the same level of water saturation as in direct water immersion or in a saturated atmosphere. What controls the water concentration in the polymer is the ratio C/Cs of water concentrations in the organic phase, where Cs is the equilibrium concentration, which can be very low but not zero. In other words, hydrophobic surface treatments can delay the time to reach sorption equilibrium but they cannot avoid the water absorption by the substrate. 

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