Nonpolar droplets

At this point in the reverse relaxation, the only aligned species that remain are the linear clusters composed of nonpolarized droplets. Their slow orientational randomization or delinearization occurs at a rate characterized by t-., [41]. 

The properties of these systems were studied with the experimental methods that we have already mentioned earlier in this chapter (1) the rheological properties of the interfacial layers using the torsion pendulum device (Figure 4.11) (2) the investigation of the compression of two nonpolar droplets immersed in an aqueous surfactant solution and the measurement of the force, Xoai. necessary for their coalescence and (3) the estimation of the free energy of interaction between... 

Several independent experimental methods were applied that allowed comparison of the properties of these systems [ 18-20]. We present only the principal results of the three foDowing approaches (i) rheological studies of interfacial adsorption layers (lAL) by the rotating suspension method (ii) observation of the compression of two nonpolar droplets in the surfactant aqueous solution, with measurement of the force needed for their coalescence and (iii) evaluation of the free energy of interaction between nonpolar groups of lAL and various nonpolar liquids by measuring the contact rupture force between two methylated (or fluorinated) smooth solid particles in a given liquid. 

Figure 3.3 Scheme of the device for compressing and coalescence of two nonpolar droplets and for rupturing the resulting one in aqueous surfactant solution. Droplets a and b are fixed within a container (5) at the end faces of cylindrical holders (3 and 2) that are connected, respectively, to a manipulator (4) and the coil... 

Dispersions. In phenoHc resin dispersions, the continuous phase is water or a nonpolar hydrocarbon solvent. The resin exists as droplets that have particle sizes of 1—20 p.m and are dispersed in the continuous phase. Aqueous dispersions are prepared either in situ during the preparation of the resin itself or by high shear mixing (25,35). 

It follows from the second law of thermodynamics that the optimal free energy of a hydrocarbon-water mixture is a function of both maximal enthalpy (from hydrogen bonding) and minimum entropy (maximum degrees of freedom). Thus, nonpolar molecules tend to form droplets with minimal exposed surface area, reducing the number of water molecules affected. For the same reason, in the aqueous environment of the hving cell the hydrophobic portions of biopolymers tend to be buried inside the structure of the molecule, or within a lipid bilayer, minimizing contact with water. 

In the past few years, a range of solvation dynamics experiments have been demonstrated for reverse micellar systems. Reverse micelles form when a polar solvent is sequestered by surfactant molecules in a continuous nonpolar solvent. The interaction of the surfactant polar headgroups with the polar solvent can result in the formation of a well-defined solvent pool. Many different kinds of surfactants have been used to form reverse micelles. However, the structure and dynamics of reverse micelles created with Aerosol-OT (AOT) have been most frequently studied. AOT reverse micelles are monodisperse, spherical water droplets [32]. The micellar size is directly related to the water volume-to-surfactant surface area ratio defined as the molar ratio of water to AOT,... 

Water-in-oil microemulsions (w/o-MEs), also known as reverse micelles, provide what appears to be a very unique and well-suited medium for solubilizing proteins, amino acids, and other biological molecules in a nonpolar medium. The medium consists of small aqueous-polar nanodroplets dispersed in an apolar bulk phase by surfactants (Fig. 1). Moreover, the droplet size is on the same order of magnitude as the encapsulated enzyme molecules. Typically, the medium is quite dynamic, with droplets spontaneously coalescing, exchanging materials, and reforming on the order of microseconds. Such small droplets yield a large amount of interfacial area. For many surfactants, the size of the dispersed aqueous nanodroplets is directly proportional to the water-surfactant mole ratio, also known as w. Several reviews have been written which provide more detailed discussion of the physical properties of microemulsions [1-3]. 

The relatively nonpolar squaraine rotaxane 14c was found to interact with cells in a very similar way to the well-known lipophilic dye Nile Red this probe rapidly accumulates at lipophilic sites inside a living cell, such as the endoplasmic reticulum and intracellular lipid droplets [55], The red emission band for probe 14c is quite narrow and permits the acquisition of multicolor images. It displayed high chemical stability and low toxicity. 

While it has been known for years that water droplets in the micrometer size range can supercool down to -40°C (Fletcher, 1962 Rasmusse et al, 1973), very few attempts have been carried out on water droplets in the nanometer range, which are obtained with micromicellar solutions of water in a number of nonpolar solvents of very low freezing point. Such solutions are homogeneous and of low viscosity they can remain perfectly colorless and therefore optically transparent at very low temperature (s-60 C) and can be used as media to investigate enzyme-catalyzed reactions. 

Colloidal liquid aphrons (CLAs), obtained by diluting a polyaphron phase, are postulated to consist of a solvent droplet encapsulated in a thin aqueous film ( soapy-shell ), a structure that is stabilized by the presence of a mixture of nonionic and ionic surfactants [57]. Since Sebba s original reports on biliquid foams [58] and subsequently minute oil droplets encapsulated in a water film [59], these structures have been investigated for use in predispersed solvent extraction (PDSE) processes. Because of a favorable partition coefficient for nonpolar solutes between the oil core of the CLA and a dilute aqueous solution, aphrons have been successfully applied to the extraction of antibiotics [60] and organic pollutants such as dichlorobenzene [61] and 3,4-dichloroaniline [62]. 

When soap is dispersed in a nonpolar phase, inverted micelles are formed in which the nonpolar tails of the soap molecules interact with the bulk solvent while the hydrophilic heads interact with each other. This behavior of amphiphilic molecules explains how they can disperse nonpolar particles in water the hydrocarbon tail of the amphiphile interacts with the particle, such as an oil droplet, dirt, or a lipoprotein membrane fragment, covers the particle, and then presents its hydrophilic head groups to the aqueous phase. 

R-groups, which act much like droplets of oil that coalesce in an aqueous environment. The nonpolar R-groups thus fill up the inte rior of the folded protein and help give it its three-dimensional shape. [Note In proteins that are located in a hydrophobic envi ronment, such as a membrane, the nonpolar R-groups are found on the outside surface of the protein, interacting with the lipid environment (see Figure 1.4).] The importance of these hydrophobic interactions in stabilizing protein structure is dis cussed on p. 19. 

Anode solution contains an alcohol, a base, S02, I-, and possibly another oiganic solvent. Methanol and diethylene glycol monomethyl ether (CH3OCH2CH2OCH2CH2OH) are typical alcohols. Typical bases are imidazole and diethanolamine. The organic solvent may contain chloroform, formamide, or other solvents. The trend is to avoid chlorinated solvents because of their environmental hazards. When analyzing nonpolar substances such as transformer oil, sufficient solvent, such as chloroform, should be used to make the reaction homogeneous. Otherwise, moisture trapped in oily emulsions is inaccessible. (An emulsion is a fine suspension of liquid-phase droplets in another liquid.)... 

In the previous section, we demonstrated the micrometer droplet size dependence of the ET rate across a microdroplet/water interface. Beside ET reactions, interfacial mass transfer (MT) processes are also expected to depend on the droplet size. MT of ions across a polarized liquid/liquid interface have been studied by various electrochemical techniques [9-15,87], However, the techniques are disadvantageous to obtain an inside look at MT across a microspherical liquid/liquid interface, since the shape of the spherical interface varies by the change in an interfacial tension during electrochemical measurements. Direct measurements of single droplets possessing a nonpolarized liquid/liquid interface are necessary to elucidate the interfacial MT processes. On the basis of the laser trapping-electrochemistry technique, we discuss MT processes of ferrocene derivatives (FeCp-X) across a micro-oil-droplet/water interface in detail and demonstrate a droplet size dependence of the MT rate. 

Since Ostwald ripening is a function of the solubility of the dispersed phase, the addition of a second nonpolar lipid with a substantially lower solubility to the high-solubility dispersed phase can strongly reduce the growth of droplets. 

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