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Handbook of Size Exclusion Chromatography and Related ...

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<strong>and</strong> Mzþ1) <strong>and</strong> polydispersity <strong>of</strong> the original sample <strong>and</strong> its fractions were<br />

determined by high-performance aqueous SEC using Ultrahydrogel columns.<br />

Preparative SEC using a Superdex column with 0.1 M NaOH as eluent has<br />

been used in investigations <strong>of</strong> MMDs <strong>of</strong> native lignins obtained by ball milling <strong>and</strong><br />

enzymatic hydrolysis (63). The preparatively obtained fractions were precipitated<br />

<strong>and</strong> characterized. The results were compared to those obtained earlier for kraft<br />

pulps <strong>and</strong> it was suggested that at least a part <strong>of</strong> the high molar mass fraction in<br />

pulp residual lignin originates from native lignin galactan complexes.<br />

The MMD <strong>and</strong> structures <strong>of</strong> lignins dissolved during organosolv<br />

delignification <strong>of</strong> eucalyptus batch <strong>and</strong> successive processes were investigated at<br />

various reaction times (64) <strong>and</strong> the possible occurrence <strong>of</strong> topochemical effects<br />

was considered.<br />

The MMD <strong>of</strong> kraft lignin in alkaline solution (65) has also been investigated<br />

by calibrated ultrafiltration membranes. The membranes were first tested with<br />

probe macromolecules to obtain sieving curves at the same conditions as the lignin<br />

analyses. It was seen that the results were different from the nominal cut-<strong>of</strong>f values<br />

when the MMD <strong>of</strong> a lignin sample was fractionated into five different fractions at<br />

pH 13.0. The SEC results confirmed the calibrated cut-<strong>of</strong>f values for the MMD.<br />

The effect <strong>of</strong> pulping variables on the MM <strong>and</strong> MMD <strong>of</strong> dissolved kraft lignin<br />

prepared by cooking slash pine (Pinus caribaea) wood chips in a pilot-scale batch<br />

circulation digester was investigated (66). The effect <strong>of</strong> four pulping parameters on<br />

the MM <strong>of</strong> dissolved lignin was examined. Generally, the MM <strong>of</strong> dissolved lignin<br />

increased in both bulk <strong>and</strong> final phases as the delignification proceeded. Prolonged<br />

cooking at the end <strong>of</strong> the final phase delignification caused degradation <strong>of</strong> lignin in<br />

the liquor <strong>and</strong> decreased its MM. The MMD <strong>of</strong> lignin- <strong>and</strong> xylan-containing<br />

macromolecules that were isolated from kraft pulps derived from aspen <strong>and</strong> spruce<br />

have been determined using SEC under highly alkaline conditions (67). The<br />

changes in MMD as a result <strong>of</strong> treatment with xylanase <strong>and</strong> under acid conditions<br />

were evaluated in order to examine the role <strong>of</strong> lignin–carbohydrate complexes in<br />

enzyme prebleaching <strong>of</strong> kraft pulp. The MM <strong>and</strong> MMD <strong>of</strong> kenaf bast <strong>and</strong> core<br />

lignin during kraft pulping were determined together with the polydispersity <strong>and</strong><br />

intrinsic viscosity, which increased with increasing cooking time (68). The MMD<br />

indicated the presence <strong>of</strong> only one component <strong>of</strong> high or low MM in the enzyme<br />

lignin <strong>of</strong> kenaf bast <strong>and</strong> core. Both the MM <strong>and</strong> polydispersity index <strong>of</strong> lignin in<br />

kenaf core were higher than those in kenaf bast under the same cooking condition,<br />

so the kenaf bast was easier to delignify than kenaf core.<br />

In investigations <strong>of</strong> the delignification processes <strong>of</strong> Eucalyptus gr<strong>and</strong>is<br />

wood the MMD <strong>of</strong> isolated native lignin, organosolv lignin, <strong>and</strong> kraft lignin were<br />

determined by an HP/SEC system (69). The weight-average MM (Mw) <strong>of</strong>the<br />

lignins decreased in the order MWL . organosolv lignin . kraft lignin. The<br />

weight-average MM decreased with increasing degree <strong>of</strong> delignification measured<br />

as the amount <strong>of</strong> extracted lignin.<br />

© 2004 by Marcel Dekker, Inc.

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