Macromolecules fractionation

The natural biopolymers, to which HA belongs, are not polydispersed polymers due to the matrix nature of their synthesis. The nature of the biochemical synthesis is determined by the matrix the enzyme upon which the triopolymer is synthesized. Nevertheless, during biopolymer extraction and purification processes they degrade in one way or another. For example, polygalactomannan, different types of cellulose (wood or cotton), chitosan and hyaluronan are isolated as a wide range of the relatively narrow dispersed macromolecule fractions. 

Fig. XV-1. Plots of t/CRT vs. C for a fractionated poly(methyl acrylate) polymer at the indicated temperatures in degrees Celsius. [From A. Takahashi, A. Yoshida, and M. Kawaguchi, Macromolecules, 15, 1196 (1982) (Ref. 1). Copyright 1982, American Chemical Society.]...

Because of the rotation of the N—N bond, X-500 is considerably more flexible than the polyamides discussed above. A higher polymer volume fraction is required for an anisotropic phase to appear. In solution, the X-500 polymer is not anisotropic at rest but becomes so when sheared. The characteristic viscosity anomaly which occurs at the onset of Hquid crystal formation appears only at higher shear rates for X-500. The critical volume fraction ( ) shifts to lower polymer concentrations under conditions of greater shear (32). The mechanical orientation that is necessary for Hquid crystal formation must occur during the spinning process which enhances the alignment of the macromolecules. 

The compositional distribution of ethylene copolymers represents relative contributions of macromolecules with different comonomer contents to a given resin. Compositional distributions of PE resins, however, are measured either by temperature-rising elution fractionation (tref) or, semiquantitatively, by differential scanning calorimetry (dsc). Table 2 shows some correlations between the commercially used PE characterization parameters and the stmctural properties of ethylene polymers used in polymer chemistry. 

Laue Method for Macromolecule X-Ray Diffraction. As indicated above it is possible to determine the stmctures of macromolecules from x-ray diffraction however, it normally takes a relatively long period of data collection time (even at synchrotrons) to collect all of the data. A new technique, the Laue method, can be used to collect all of the data in a fraction of a second. Instead of using monochromated x-rays, a wide spectmm of incident x-rays is used. In this case, all of the reflections that ate diffracted on to an area detector are recorded at just one setting of the detector and the crystal. By collecting many complete data sets over a short period of time, the Laue method can be used to foUow the reaction of an enzyme with its substrate. This technique caimot be used with conventional x-ray sources. 

Albertsson (Paiiition of Cell Paiiicle.s and Macromolecules, 3d ed., Wiley, New York, 1986) has extensively used particle distribution to fractionate mixtures of biological products. In order to demonstrate the versatility of particle distribution, he has cited the example shown in Table 22-14. The feed mixture consisted of polystyrene particles, red blood cells, starch, and cellulose. Liquid-liquid particle distribution has also been studied by using mineral-matter particles (average diameter = 5.5 Im) extracted from a coal liquid as the solid in a xylene-water system [Prudich and Heniy, Am. Inst. Chem. Eng. J., 24(5), 788 (1978)]. By using surface-active agents in order to enhance the water wettability of the solid particles, recoveries of better than 95 percent of the particles to the water phase were obsei ved. All particles remained in the xylene when no surfactant was added. 

Autofiltration The retention of any material at the surface of the membrane gives rise to the possibility of a secondaiy or a dynamic membrane being formed. This is a significant problem for fractionation by ultrafiltration because microsolutes are partially retained by almost all retained macrosolutes. The degree of retention is quite case-specific. As a rule of thumb, higher pressure and more polarization resiilts in more autofiltration. Autofiltration is particularly problematic in attempts to fractionate macromolecules. 

Figure 2. Phase diagram for PEO-LiN(CF,S03)2 showing the eutectic equilibrum between PEO (Mw =4xI06) ant the 6 1 (salt wt. Fraction 0.52) intermediate compound. Compiled from C. I. abreche, I. Levesque, J. Prud homme, Macromolecule 1996, 29, 7795 and S. Lascaud, M. Perrier, A. Vallee, S. Besner, J. Prud homme, M. Armand, Macromolecules 1994, 27, 7469.

An affinity sorbent based on WPA-PG carrying immobilized human IgG was applied to the isolation of the first component of the complement (Cl) from human serum and for its separation into subcomponents Clr, Cls and Clq by the one-step procedure [126,127]. Cl was quantitatively bound to the sorbent at 0 °C. The activities of subcomponents Clq and Clr2r2 in the unbound part of the serum were found to be 0.8% and 3.3% of the initial activities in serum. This fraction, therefore, could be used as a R1 reagent for determining the hemolytic activity of Cl. Apparently, the neighboring macromolecules of immobilized IgG resemble to some extent an immune complex, whereas Cl formation is facilitated due to the mobility of polymer chains with the attached IgG macromolecules (Cl is usually dissociated in serum by 30%). After activation of bound Cl by heating (30 °C, 40 min) the activated subcomponent Clr is eluted from the sorbent. Stepwise elution with 0.05 mol/1 EDTA at pH 7.4 or with 0.05 mol/1 EDTA + 1 mol/1 NaCl at pH 8.5 results in a selective and quantitative elution of the activated subcomponent Cls and subcomponent Clq. 

The fraction of macromolecules which have been degraded ( ) is equal to the volume of all the fluid elements which satisfy Eq. (102) divided by the total flow across the orifice. Assuming a constant velocity profile at the orifice, in this case is just equal to (r/r0)2, with r0 being the radius of the orifice. 

It was shown 15,161 that, as the filler-volume fraction is increased, the proportion of macromolecules, participating in this boundary layers with reduced mobilities, is also increased, so that the number of macromolecules participating in the Tg-process is reduced. This is equivalent to a relative increase of ur... 

A way to narrow the MWD and to approach the structure of dendrimers is the addition of a small fraction of a/-functional initiator, to inimers [40,71]. In this process the obtainable degree of polymerization is limited by the ratio of inimer to initiator. It can be conducted in two ways (i) inimer molecules can be added so slowly to the initiator solution that they can only react with the initiator molecules or with the already formed macromolecules, but not with each other (semi-batch process). Thus, each macromolecule generated in such a process will contain one initiator core but no vinyl group. Then, the polydispersity index is quite low and decreases with / M /Mn l-i-l//. (ii) Alternatively, initiator and monomer molecules can be mixed instantaneously (batch process). Here, the normal SCVP process and the process shown above compete and both kinds of macromolecules will be formed. For this process the polydispersity index also decreases with/,but is higher than for the semi-batch process, M /Mn=Pn//. ... 

Field-Flow Fractionation Analysis of Macromolecules and Particles,... 

Buesseler KO, Bauer JE, Chen RF, Eglinton TI, Gustafsson O, Landing W, Mopper K, Moran SB, Santschi PH, Vernon Clark R, Wells ML (1996) An intercomparison of cross-flow filtration techniques used for sampling marine colloids overview and organic carbon results. Marine Chem 55 1-31 Buffle J, Perret D, Newman M (1992) The use of filtration and ultrafiltration for size fractionation of aquatic particles, colloids, and macromolecules. In Enviroiunental particles. Buffle J, van Leeuwen HP (eds) Lewis Publishers, Boca Raton FL, pl71-230... 

Firstly, some of the important characteristics of the performance properties of copolymers can be expressed through the fractions of these sequences. So, for example, dealing with copolymers they normally make extensive use of semiempiri-cal relationships relating the glass transition temperature, T , with the fractions of dyads in macromolecules [7]. The simplest of such relationships reads ... 

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