Globular solutes

The neutral hydrophilic surface and the wide range of pore diameters available for SynChropak GPC allow many compounds from small peptides to nucleic acids and other polymers to be analyzed. Table 10.2 lists the approximate exclusion limits for both linear and globular solutes. Although this information... 

The retention properties of ultrafiltration membranes are expressed as Molecular Weight Cutoff (MWCO). This value refers to the approximate molecular weight (MW) of a dilute globular solute (i.e., a typical protein) which is 90% retained by the membrane. However, a molecule s shape can have a direct effect on its retention by a membrane. For example, linear molecules like DNA may find their way through pores that will retain a globular species of the same molecular weight. 

S. A. Safran, Theory of Structure and Phase Transitions in Globular Microemulsions, in Micellar Solutions and Microemulsions, S. H. Chen and R. Rajagopalan, eds.. Springer-Verlag, New York, 1990, Chapter 9. 

Materials have many properties that are important, scientifically and teclmologically, that do not depend on the details of long-range stnicture. For example, consider a solution of globular macromolecules in a solvent... 

The behaviour of tliese systems is similar to tliat of suspensions in which short-range attractions are induced by changing solvent quality for sterically stabilized particles (e.g. [103]). Anotlier case in which narrow attractions arise is tliat of solutions of globular proteins. These crystallize only in a narrow range of concentrations [104]. 

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. 

Equation (8.97) shows that the second virial coefficient is a measure of the excluded volume of the solute according to the model we have considered. From the assumption that solute molecules come into surface contact in defining the excluded volume, it is apparent that this concept is easier to apply to, say, compact protein molecules in which hydrogen bonding and disulfide bridges maintain the tertiary structure (see Sec. 1.4) than to random coils. We shall return to the latter presently, but for now let us consider the application of Eq. (8.97) to a globular protein. This is the objective of the following example. 

The Stokes-Einstein equation has already been presented. It was noted that its vahdity was restricted to large solutes, such as spherical macromolecules and particles in a continuum solvent. The equation has also been found to predict accurately the diffusion coefficient of spherical latex particles and globular proteins. Corrections to Stokes-Einstein for molecules approximating spheroids is given by Tanford. Since solute-solute interactions are ignored in this theory, it applies in the dilute range only. 

Anionic and neutral polymers are usually analyzed successfully on Syn-Chropak GPC columns because they have minimal interaction with the appropriate mobile-phase selection however, cationic polymers adsorb to these columns, often irreversibly. Mobile-phase selection for hydrophilic polymers is similar to that for proteins but the solubilities are of primary importance. Organic solvents can be added to the mobile phase to increase solubility. In polymer analysis, ionic strength and pH can change the shape of the solute from mostly linear to globular therefore, it is very important to use the same conditions during calibration and analysis of unknowns (8). Many mobile phases have been used, but 0.05-0.2 M sodium sulfate or sodium nitrate is common. 

Mobile-phase selection for cationic polymers is similar to that for the other polymers in that ionic strength and pH can change the shape of the solute from linear to globular (9). Mobile phases are often low pH e.g., 0.1% trifluo-roacetic acid, including 0.2 M sodium chloride, has been used successfully for polyvinylpyridines. Sodium nitrate can be substituted for the chloride to avoid corrosive effects. Some salt must be included so that ion exclusion does not occur (3). 

The morphology of globular type is the most favourable when superplastic deformation is to occur in AI78wt%Zn alloy. This type of structure is formed by decomposition of the a solid solution a -> a + P However, plates usually dominate in the structure of this alloy. To obtain the non-plate or globular type, a special heat treatment is neccesary i.e. the optimal cooling rate as well as the temperature and time of ageing. 

The logarithm of the micellar molecular weight (M) and consequently the aggregation number of sodium dodecyl sulfate at 25°C in aqueous sodium chloride solutions is linearly related to the logarithm of the CMC plus the concentration of salt (Cs), both expressed in molar units, through two equations [116]. Below 0.45 M NaCl micelles are spherical or globular, and Eq. (18) applies ... 

Tanford, Charles. The electrostatic free energy of globular protein ions in aqueous salt solution. Journal of Physical Chemistry 59 (1955) 788-793. 

Globular proteins are known to act as polymeric stabilizers of protein structure in solution. Wang and Hanson [106] review the mechanisms of protein stabilization by serum albumin, and it has been included in... 

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