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A novel thermally-activated crosslinking agent for chitosan in aqueous solution: a rheological investigation

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Abstract.

The use of 2,5-dimethoxy-2,5-dihydrofuran (DHF) as a temperature-controlled gelation agent for chitosan under acidic conditions has been examined by dynamic oscillatory and viscometry techniques. In particular, the rate and extent of gelation have been examined over a range of different temperatures (40–98 °C), DHF concentrations (10–100 mM) and pH conditions (0.9–2.1). The gelation time, tG, decreases, and the maximum gelation rate increases substantially as a function of rising temperature. When fit with a simple Arrhenius function, the tG data yield an activation energy for gelation of 55±8 kJ mol-1. Gelation is found to occur on the shortest time-scale, and the strongest gels result, at the highest DHF concentrations investigated. Similarly, the gelation rate and gel strength are highest for the most acidic solution conditions examined. Experimental findings are interpreted in terms of a competition between the crosslinking reaction (which drives gel formation, and is initially dominant) and protolytic decomposition of chitosan (which disrupts the gel structure, and becomes increasingly important as time progresses). Syneresis phenomena additionally impact results obtained at DHF concentrations ≥50 mM.

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Notes

  1. The strict definition of tG has been considered in detail by Chambon and Winter [75, 76, 77], who defined it as the condition at which tan(G’’/G’) is independent of frequency. Their treatment requires accurate measurements of G’ and G’’ over a wide range of frequencies both before and after tG and additionally, requires that G’ and G’’ do not vary appreciably during each frequency sweep. Unfortunately, in the present study, G’ and G’’ were difficult to accurately assess prior to tG due to measurements being undertaken at the lower stress limit of the rheometer. In addition, during the gelation process, G’ and G’’ were often found to vary significantly over the duration of each frequency sweep. As a result, tG could not be accurately assessed using the treatment of Chambon and Winter [75, 76, 77]. The G’-G’’ crossover method of Tung and Dynes [78] was instead used and, while not providing a strict measure of tG, does allow a comparison of the crosslinking behaviour at a common stage of gelation. It is, however, worthy of note that given the change in δ from ca. 80° to ≤1° is rapid, particularly at the higher temperatures investigated (see Fig. 2), it is expected that the values of tG calculated using the G’-G’’ crossover method are in reasonable agreement with the Chambon and Winter gel point definition.

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Acknowledgements.

Financial support for this work provided through the Australian Research Council’s Small Grants program.

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Authors and Affiliations

  1. Department of Geological and Environmental Sciences, Stanford University, Building 320, Stanford, CA, 94305–2115, USA

    Stephen B. Johnson

  2. Department of Chemical Engineering, University of Melbourne, Parkville, Victoria 3010, Australia

    David E. Dunstan

  3. Department of Chemical Engineering, University of Newcastle, Callaghan, New South Wales 2308, Australia

    George V. Franks

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  1. Stephen B. Johnson
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  2. David E. Dunstan
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  3. George V. Franks
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Correspondence to George V. Franks.

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Johnson, S.B., Dunstan, D.E. & Franks, G.V. A novel thermally-activated crosslinking agent for chitosan in aqueous solution: a rheological investigation. Colloid Polym Sci 282, 602–612 (2004). https://doi.org/10.1007/s00396-003-0985-z

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