Macromolecules charge

Labille, J.,Thomas, F., Milas, M., and Vanhaverbeke, C. (2005). Flocculation of colloidal clay by bacterial polysaccharides Effect of macromolecule charge and structure. /. Coll. Interface Sci. 284,149-156. 

Apart from polymer adsorption for uncharged macromolecules, charged macromolecules (polyelectrolytes), such as proteins can also adsorb at surfaces [20, 21]. Adsorption of a charged macromolecule is different from adsorption of an uncharged polymer in that there is a high dependency on the salt concentration. At a low salt concentration, repulsive electrostatic forces between charged polymer chains will inhibit formation of loops and tails (Fig. 4). This has been predicted and confirmed, for instance for adsorption of humic acids on iron-oxide particles [22]. 

Clearly, the concentrations inside cannot be equal to the bulk solution values because of the macromolecule charge, the cation concentration should be higher than the bulk, whereas the anion concentration should be lower. The ions able to cross the membrane must be in electrochemical (osmotic) equilibrium between the two solutions that is, in Equations 3.1 through 3.3, the electrochemical potentials must be equal. 

Elution chromatography based on liquid-solid adsorption for small molecules typically employs adsorbents such as alumina, charcoal, silica, hydrophobic silica, etc. Surface area, water content and the chemical nature of the adsorbent (e.g. polar or nonpolar) distinguisb one adsorbent from another. For larger molecules/macromolecules/charged species, other adsorbents needed are briefly touched upon in Sections 7.1.5.1.6-7.1.5.1.8. 

When this equation is applied to a system composed of a macromolecule immersed in an aqueous medium containing a dissolved electrolyte, the fixed partial charges of each atom of the macromolecule result in a charge density described by p, and the mobile charges of the dissolved electrolyte are described by /O , which i derived from a Boltzmann distribution of the ions and coions. 

Another way of calculating the electrostatic component of solvation uses the Poisson-Boltzmann equations [22, 23]. This formalism, which is also frequently applied to biological macromolecules, treats the solvent as a high-dielectric continuum, whereas the solute is considered as an array of point charges in a constant, low-dielectric medium. Changes of the potential within a medium with the dielectric constant e can be related to the charge density p according to the Poisson equation (Eq. (41)). 

The final class of methods that we shall consider for calculating the electrostatic compone of the solvation free energy are based upon the Poisson or the Poisson-Boltzmann equatior Ihese methods have been particularly useful for investigating the electrostatic properties biological macromolecules such as proteins and DNA. The solute is treated as a body of co stant low dielectric (usually between 2 and 4), and the solvent is modelled as a continuum high dielectric. The Poisson equation relates the variation in the potential (f> within a mediu of uniform dielectric constant e to the charge density p ... 

Coa.cerva.tlon, A phenomenon associated with coUoids wherein dispersed particles separate from solution to form a second Hquid phase is termed coacervation. Gelatin solutions form coacervates with the addition of salt such as sodium sulfate [7757-82-6] especially at pH below the isoionic point. In addition, gelatin solutions coacervate with solutions of oppositely charged polymers or macromolecules such as acacia. This property is useful for microencapsulation and photographic apphcations (56—61). 

Several devices are available commercially to measure mobihty. One of these (Zeta-Meter Inc., New York) allows direct microscopic measurement of individual particles. Another allows measurement in more concentrated suspensions (Numinco Instrument Corp., Monroeville, Pa.). The state of the charge can also be measured by a streaming-current detecdor (Waters Associates, Inc., Framingham, Mass.). For macromolecules, more elaborate devices such as the Tisehus moving-boundaiy apparatus are used. 

A very simple version of this approach was used in early applications. An alchemical charging calculation was done using a distance-based cutoff for electrostatic interactions, either with a finite or a periodic model. Then a cut-off correction equal to the Born free energy, Eq. (38), was added, with the spherical radius taken to be = R. This is a convenient but ill-defined approximation, because the system with a cutoff is not equivalent to a spherical charge of radius R. A more rigorous cutoff correction was derived recently that is applicable to sufficiently homogeneous systems [54] but appears to be impractical for macromolecules in solution. 

Charged macromolecules, such as proteins or polymers, are often separated elec-trophoretically. The rate of migration through an electric field increases with net charge and field strength. Molecular size of analytes and viscosity of separation media both have inverse relationships with rate of migration. These variables must all be taken into account in order to optimize the conditions for an efficient electrophoretic separation. 

Graft Copolymerization of Vinyl Monomers Onto Macromolecules Having Active Pendant Group via Ceric Ion Redox or Photo-Induced Charge-Transfer Initiation... 

MACROMOLECULES HAVING AN ACTIVE PENDANT GROUP BY PHOTO-INDUCED CHARGE-TRANSFER INITIATION... 

Therefore, the graft copolymerization of vinyl monomers onto macromolecules having active an pendant group can be achieved either by redox initiation with a Ce(IV) ion or by photo-induced charge-transfer initiation with BP, depending on the structure of the active groups. 

High sorption capacities with respect to protein macromolecules are observed when highly permeable macro- and heteroreticular polyelectrolytes (biosorbents) are used. In buffer solutions a typical picture of interaction between ions with opposite charges fixed on CP and counterions in solution is observed. As shown in Fig. 13, in the acid range proteins are not bonded by carboxylic CP because the ionization of their ionogenic groups is suppressed. The amount of bound protein decreases at high pH values of the solution because dipolar ions proteins are transformed into polyanions and electrostatic repulsion is operative. The sorption maximum is either near the isoelectric point of the protein or depends on the ratio of the pi of the protein to the pKa=0 5 of the carboxylic polyelectrolyte [63]. It should be noted that this picture may be profoundly affected by the mechanism of interaction between CP and dipolar ions similar to that describedby Eq. (3.7). 

The transfer of PCSs from solutions into the solid state may be accompanied by the origination of hydrogen and salt bonds, by associations in crystalline regions, or by charge transfer states and some other phenomena. These effects are followed by some conformational transformations in the macromolecules. The solution of the problem of the influence of these phenomena on the conjugation efficiency and on the complex of properties of the polymer is of fundamental importance. 

Due to the fact that the nitrile groups interact with the positively charged carbon atoms of the carboxyl or ester groups more easily than the less mobile nitrile groups in the PAN macromolecules interact with each other, the electrophilicity of the nitrile groups in the macromolecules of the copolymers increases to a greater extent, which, naturally, manifests itself in the increase of the rate of hydrogen sulfide addition. 

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