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Handbook of Size Exclusion Chromatography and Related ...

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Also <strong>of</strong> note in Fig. 13b is how highly the scattering is suppressed when SDS is<br />

present with the PVP in asalt-free solution. This is again amanifestation <strong>of</strong> the<br />

electrostatically enhanced A2 due to the electrical charging <strong>of</strong> PVP by SDS.<br />

In contrast, when such a solution is exposed to salt (e.g., 0.1M NaCl in<br />

Fig. 13b) the scattering is actually higher than when no SDS is present,<br />

reflecting the fact that A2 has been greatly lowered by the NaCl, <strong>and</strong> that the<br />

mass <strong>of</strong> the complex formed by SDS <strong>and</strong> PVP is significantly greater than the<br />

mass <strong>of</strong> the PVP alone.<br />

Figure 14 shows how these two latter factors are affected by salt. A<br />

procedure for determining the mass ratio <strong>of</strong> SDS to PVP in the aggregates r, was<br />

presented in Ref. 7. Figure 14 shows that r increases from 0.6 to 1.6 as [NaCl]<br />

increases, for PVP under saturating SDS conditions, due to the decrease in<br />

repulsion among the charged SDS groups. A significant decrease in A2 from<br />

0.0022 to 0.0003 is also seen as [NaCl] increases.<br />

4 SUMMARY<br />

Use <strong>of</strong> automatic continuous mixing, together with multiple detectors provides<br />

state-<strong>of</strong>-the-art characterization for polymers in a variety <strong>of</strong> equilibrium <strong>and</strong><br />

nonequilibrium contexts. ACOMP is one <strong>of</strong> the ACM family <strong>of</strong> techniques that<br />

promises the greatest long-term economic impact, both in terms <strong>of</strong> fundamental<br />

research <strong>and</strong> on-line reactor control. ACOMP is rapidly being adapted to a wide<br />

variety <strong>of</strong> polymerization reaction contexts, including batch <strong>and</strong> continuous<br />

reactors, homogeneous <strong>and</strong> inhomogeneous media, <strong>and</strong> those that produce<br />

slurries, pellets, <strong>and</strong> phase-separated products. Significant improvement in<br />

the front end, involving the ACM portion, is expected to augment greatly the<br />

versatility <strong>of</strong> ACOMP.<br />

ACM should steadily find new monitoring applications for degradation,<br />

aggregation, microcrystallization, <strong>and</strong> other phase-separation processes. ACM in<br />

the equilibrium characterization milieu should prove to be immensely labor<br />

saving, especially for the study <strong>of</strong> complex systems, such as those involving<br />

polyelectrolytes, salts, <strong>and</strong> surfactant agents.<br />

Also on the horizon is a new application for light scattering; simultaneous<br />

multiple sample light scattering, or SMSLS (74). This takes advantage <strong>of</strong> the<br />

greatly lowered expense <strong>of</strong> light-scattering sample cells (75), laser light, <strong>and</strong><br />

sensitive photodetection to gang many independent cells together to form an<br />

instrument unified under the control <strong>of</strong> a single computer. Applications are<br />

expected in combinatorial <strong>and</strong> high-throughput methods applied to new polymer<br />

synthesis (76–78), shelf-life <strong>and</strong> stability measurements, aggregation, dissolution,<br />

<strong>and</strong> multiple reactor sampling.<br />

© 2004 by Marcel Dekker, Inc.

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