Ellipsoids

Other techniques such as X-ray diffusion or small angle neutron diffusion are also used in attempts to describe the size and form of asphaltenes in crude oil. It is generally believed that asphaltenes have the approximate form of very flat ellipsoids whose thicknesses are on the order of one nanometer and diameters of several dozen nanometers. 

Micellar structure has been a subject of much discussion [104]. Early proposals for spherical [159] and lamellar [160] micelles may both have merit. A schematic of a spherical micelle and a unilamellar vesicle is shown in Fig. Xni-11. In addition to the most common spherical micelles, scattering and microscopy experiments have shown the existence of rodlike [161, 162], disklike [163], threadlike [132] and even quadmple-helix [164] structures. Lattice models (see Fig. XIII-12) by Leermakers and Scheutjens have confirmed and characterized the properties of spherical and membrane like micelles [165]. Similar analyses exist for micelles formed by diblock copolymers in a selective solvent [166]. Other shapes proposed include ellipsoidal [167] and a sphere-to-cylinder transition [168]. Fluorescence depolarization and NMR studies both point to a rather fluid micellar core consistent with the disorder implied by Fig. Xm-12. 

It has been shown that spherical particles with a distribution of sizes produce diffraction patterns that are indistingiushable from those produced by triaxial ellipsoids. It is therefore possible to assume a shape and detemiine a size distribution, or to assume a size distribution and detemiine a shape, but not both simultaneously. 

Woessner D E 1962 Nuclear spin relaxation in ellipsoids undergoing rotational Brownian motion J. Chem. Rhys. 37 647-54... 

Camp P J, Mason C P, Allen M P, Khare A A and Kofke D A 1996 The isotropic-nematic transition in uniaxial hard ellipsoid fluids coexistence data and the approach to the Onsager limit J. Chem. Phys. 105 2837-49... 

Frenkel D, Mulder B M and McTague J P 1984 Phase-diagram of a system of hard ellipsoids Phys. Rev.L 52 287-90... 

The spherical shell model can only account for tire major shell closings. For open shell clusters, ellipsoidal distortions occur [47], leading to subshell closings which account for the fine stmctures in figure C1.1.2(a ). The electron shell model is one of tire most successful models emerging from cluster physics. The electron shell effects are observed in many physical properties of tire simple metal clusters, including tlieir ionization potentials, electron affinities, polarizabilities and collective excitations [34]. 

Clemenger K 1985 Ellipsoidal shell struoture in free-eleotron metal olusters Phys. Rev. B 32 1359... 

It has not proved possible to develop general analytical hard-core models for liquid crystals, just as for nonnal liquids. Instead, computer simulations have played an important role in extending our understanding of the phase behaviour of hard particles. Frenkel and Mulder found that a system of hard ellipsoids can fonn a nematic phase for ratios L/D >2.5 (rods) or L/D <0.4 (discs) [73] however, such a system cannot fonn a smectic phase, as can be shown by a scaling... 

Frenkel D and Mulder B 1985 The hard ellipsoid-of-revolution fluid. 1. Monte-Carlo simulations Mol. Phys. 55 1171-92... 

The early Hartley model [2, 3] of a spherical micellar stmcture resulted, in later years, in some considerable debate. The self-consistency (inconsistency) of spherical symmetry witli molecular packing constraints was subsequently noted [4, 5 and 6]. There is now no serious question of tlie tenet tliat unswollen micelles may readily deviate from spherical geometry, and ellipsoidal geometries are now commonly reported. Many micelles are essentially spherical, however, as deduced from many light and neutron scattering studies. Even ellipsoidal objects will appear... 

A drawback of the SCRF method is its use of a spherical cavity molecules are rarely exac spherical in shape. However, a spherical representation can be a reasonable first apprc mation to the shape of many molecules. It is also possible to use an ellipsoidal cavity t may be a more appropriate shape for some molecules. For both the spherical and ellipsoi cavities analytical expressions for the first and second derivatives of the energy can derived, so enabling geometry optimisations to be performed efficiently. For these cavil it is necessary to define their size. In the case of a spherical cavity a value for the rad can be calculated from the molecular volume ... 

Rinaldi D, M F Ruiz-Lopez and J L Rivail 1983. Ab Initio SCF Calculations on Electrostatically Solvate Molecules Using a Deformable Three Axes Ellipsoidal Cavity. Journal of Chemical Physics 78 834 838. 

Hydrogen bonding stabilizes some protein molecules in helical forms, and disulfide cross-links stabilize some protein molecules in globular forms. We shall consider helical structures in Sec. 1.11 and shall learn more about ellipsoidal globular proteins in the chapters concerned with the solution properties of polymers, especially Chap. 9. Both secondary and tertiary levels of structure are also influenced by the distribution of polar and nonpolar amino acid molecules relative to the aqueous environment of the protein molecules. Nonpolar amino acids are designated in Table 1.3. 

The intrinsic viscosity of a solution of particles shaped like ellipsoids of revolution is given by the expression... 

In addition to an array of experimental methods, we also consider a more diverse assortment of polymeric systems than has been true in other chapters. Besides synthetic polymer solutions, we also consider aqueous protein solutions. The former polymers are well represented by the random coil model the latter are approximated by rigid ellipsoids or spheres. For random coils changes in the goodness of the solvent affects coil dimensions. For aqueous proteins the solvent-solute interaction results in various degrees of hydration, which also changes the size of the molecules. Hence the methods we discuss are all potential sources of information about these interactions between polymers and their solvent environments. 

The spherical geometry assumed in the Stokes and Einstein derivations gives the highly symmetrical boundary conditions favored by theoreticians. For ellipsoids of revolution having an axial ratio a/b, friction factors have been derived by F. Perrin, and the coefficient of the first-order term in Eq. (9.9) has been derived by Simha. In both cases the calculated quantities increase as the axial ratio increases above unity. For spheres, a/b = 1. 

In the last section we noted that Simha and others have derived theoretical expressions for q pl(p for rigid ellipsoids of revolution. Solving the equation of motion for this case is even more involved than for spherical particles, so we simply present the final result. Several comments are necessary to appreciate these results ... 

The totally symmetrical sphere is characterized by a single size parameter its radius. Ellipsoids of revolution are used to approximate the shape of unsymmetrical bodies. Ellipsoids of revolution are characterized by two size parameters. 

The ellipsoid of revolution is swept out by rotating an ellipse along its major or minor axis. When the major axis is the axis of rotation, the resulting rodlike figure is said to be prolate when the minor axis is the axis of rotation, the disklike figure is said to be oblate. 

We designate the length of the ellipsoid along the axis of rotation as 2a and the equatorial diameter as 2b to define the axial ratio a/b which characterizes the ellipticity of the particle. By this definition, a/b > 1 corresponds to prolate ellipsoids, and a/b < 1 to oblate ellipsoids. 

The viscosity of a suspension of ellipsoids depends on the orientation of the particle with respect to the flow streamlines. The ellipsoidal particle causes more disruption of the flow when it is perpendicular to the streamlines than when it is aligned with them the viscosity in the former case is greater than in the latter. For small particles the randomizing effect of Brownian motion is assumed to override any tendency to assume a preferred orientation in the flow. 

Based on these ideas, the intrinsic viscosity (in 0 concentration units) has been evaluated for ellipsoids of revolution. Figure 9.3 shows [77] versus a/b for oblate and prolate ellipsoids according to the Simha theory. Note that the intrinsic viscosity of serum albumin from Example 9.1-3.7(1.34) = 4.96 in volume fraction units-is also consistent with, say, a nonsolvated oblate ellipsoid of axial ratio about 5. 

Figure 9.3 Intrinsic viscosity according to the Simha theory in terms of the axial ratio for prolate and oblate ellipsoids of revolution.

At 37°C the viscosity of water is about 0.69 X 10"3 kg m" sec" the difference between this figure and the viscosity of blood is due to the dissolved solutes in the serum and the suspended cells in the blood. The latter are roughly oblate ellipsoids of revolution in shape. 

Rigid particles other than unsolvated spheres. It is easy to conclude qualitatively that either solvation or ellipticity (or both) produces a friction factor which is larger than that obtained for a nonsolvated sphere of the same mass. This conclusion is illustrated in Fig. 9.10, which shows the swelling of a sphere due to solvation and also the spherical excluded volume that an ellipsoidal particle requires to rotate through all possible orientations. 

Figure 9.10 Schematic relationship between the radius Rq of an unsolvated sphere and the effective radius R of a solvated sphere or of a spherical volume excluded by an ellipsoidal particle rotating through all directions.

The intrinsic viscosity of poly(7-benzyl-L-glutamate) (Mq = 219) shows such a strong molecular weight dependence in dimethyl formamide that the polymer was suspected to exist as a helix which approximates a prolate ellipsoid of revolution in its hydrodynamic behaviorf ... 

R/Ro)soiv(f/fo)ellip = n + (mib/m2)(P2/Pi)] (f/fo)eiiip-Briefly justify this expansion of the (f/fo oiv factor. Assuming these particles were solvated to the extent of 0.26 g water (g protein)", calculate (f/fo)eiHp-For prolate ellipsoids of revolution (b/a < 1), Perrin has derived the following expression ... 

---