Swelling phase transition

Three phenomena described above beg quantitative explanation. First, the buffer effects, which are readily explained qualitatively, require a quantitative theory. Second, the specific counterion effects need to be addressed. Third, there is the putative swelling phase transition that occurs at a critical pH, the latter depending on the composition of the geL As of this writing, only the buffer effects have been considered in detail, although work is in progress to understand the nature of the phase transition. 

The dDAVP preparations used in this study were prepared in low water contents so that the lamellar phase was formed, which in turn was injected into the rabbits. The reason for this was the fact that the lamellar phase with its mucous-like rheology is easier to inject than the stiff cubic phase. Since the lamellar phase swells into the cubic phase in excess water according to the phase diagram in Figure 1, a phase transition was expected also in the in vivo situation. The transition was found to be very fast as judged by inspection of the injection site immediately after administration. 

Fig.66 Phase diagrams of a symmetric (peo = 0.51, Mn = 2700, Mw/Mn = 1.10) and b asymmetric (0peo = 0.32, Mn = 2100, Mw/Mn = 1.14) PEO-fc-PEP block copolymers blended with epoxy resin. Phase transitions which originate from swelling of PEO chains with epoxy and/or curing agent are drawn as single lines, without implication that there are no coexistence regions. From [197]. Copyright 2001 Wiley...

Ilavsky, M. Effect on Phase Transition on Swelling and Mechanical Behavior of Synthetic Hydrogels. Vol. 109, pp. 173-206. 

Closed bilayer aggregates, formed from phospholipids (liposomes) or from surfactants (vesicles), represent one of the most sophisticated models of the biological membrane [55-58, 69, 72, 293]. Swelling of thin lipid (or surfactant) films in water results in the formation of onion-like, 1000- to 8000-A-diameter multilamellar vesicles (MLVs). Sonication of MLVs above the temperature at which they are transformed from a gel into a liquid (phase-transition temperature) leads to the formation of fairly uniform, small (300- to 600-A-diameter) unilamellar vesicles (SUVs Fig. 34). Surfactant vesicles can be considered to be spherical bags with diameters of a few hundred A and thickness of about 50 A. Typically, each vesicle contains 80,000-100,000 surfactant molecules. 

Tubules have also been prepared by swelling thin films of polymerizable diacetylenic phosphatidylhydroxyethanol (choline functionally in 21 is replaced by hydroxyethanol) in aqueous metal ion solutions above the phase transition temperature of the lipid. Various cylindrical structures were observed upon swelling the lipid in the presence of mono- and divalent cations. In contrast, no definable microstructures were noted in the absence of cations [362],... 

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