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Figure 7.10. The effect of light on the dynamic properties of physical cross-links between azobenzene-modi ed poly(acrylate) and poly(cyclodextrin). The relaxation modulus in stress relaxation experiments is plotted after application at time zero of a xed strain to a 0.7% polymer solution in water (polymer structure, cf. Fig. 7.1, with n = 11 and x = 3) with polycyclodextrin at 0.25% (lower curves) or 0.5% (higher moduli). The sample was either incubated for 24 h in the dark (dark-adapted, closed symbols) or continuously exposed to UV before and after loading in the rheometer (open symbols). Details on the samples composition are given in Pouliquen et al. (2007).
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The foregoing sections were aimed at clarifying the conditions for achieving ample photoresponses of polymer self-association (including aggregation), or association with a nanoparticle in solution. Once controlled, the formation of such associates open a vast potential for taking advantage of their properties in applications that are not limited to solution turbidity or viscosity. For instance, responsive solubility could readily help the design of light-responsive capsules, for targeted release of active compounds. In this section, we present brie y one extension of photocomplexes to the control of interfacial properties in emulsions by complex emulsi ers, namely, surfactant and photopolymer associates. Being kinetically stable, the preparation of emulsions requires vigorous mixing of oil and water in the presence of emulsi ers (amphiphiles active at oil water interfaces) such as small-molecule and polymeric surfactants. Once formed, emulsions are composed of droplets of size generally exceeding 0.1 mm dispersed within a continuous liquid. Their lifetime vary in a range of a few seconds to years. Of importance, from the well-established nonequilibrium emulsion stability pattern, we know that one should go through a critical transition region (CTR) of instability to switch the emulsion type (O/W=oil droplets in water-continuous solution, W/O=water droplets in oil continuum). Consequently, the formation of both types of emulsion is attainable from the CTR of emulsion instability by slightly changing one control parameter. This can be practically achieved by altering continuously the interfacial properties of the emulsi er(s) and, hence, their hydrophilic lipophilic balance. However, numerous attempts to develop light-responsive surfactants have shown the weak impact of the light-triggered molecular modi cation, such as transconformation or polarity changes on the energetics of interfacial properties (Cicciarelli et al., 2007; Shang et al., 2003). The properties of the surfactant molecules at the interface could, however, be triggered in more complex systems, which would amplify the effect of light. As shown earlier, the association between polymer and surfactant molecules can result in light-triggered composition of complexes, in the formation of gels or dense phases that could contribute to the interface energetics. Consequently, the following four components were selected to prepare the photoresponsive emulsion system: equal volumes of n-dodecane and 0.3 M NaNO3 aqueous solution, the C12E4 surfactant, and an azobenzene-modi ed poly(acrylate). C12E4 is known to stabilize direct and inverse emulsions below and above the so-called phase inversion temperature (PIT; here #241C), respectively. Emulsions are unstable in the vicinity of the PIT, a temperature domain corresponding to the CTR of the light-responsive system. Emulsions made of equal oil and water volumes are directly below the PIT (and display a high electric conductivity because of the water continuum), but inverse (and of low conductivity) above the PIT (Khoukh et al., 2005). In Fig. 7.11, the open triangles show that temperature can be used to generate the conductivity drop at the PIT. The emulsion sequences observed on a
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Figure 7.11. Light-responsive and reversible inversion of emulsion (dodecane/ water+NaNO3). The conductivity measurements indicate the type of continuous phase (conducting water vs. insulating oil) in samples maintained under gentle agitation (stirring bar). The emulsi er contains an azobenzene-modi ed polyacrylate (n = 5, x = 3% in Fig. 7.1) and a temperature-responsive surfactant (C12E4) that in absence of polymer would stabilize inverse emulsion above 241C. (a) Temperature sweep of the same sample exposed to UV or blue light. (b) Switches of the wavelength of exposure between UV and blue lights at xed temperature (251C) at times pointed by arrows.
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