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7.5. CONCLUSION
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temperature sweep at constant surfactant concentration (20 g/L) are essentially the same in the absence of polymer and in the presence of polymer (3 g/L) under permanent UV irradiation (365 nm). In contrast, under continuous visible irradiation (436 nm), only direct emulsions form over the whole range of temperature (Fig. 7.11a). In addition, it was possible to reversibly control the inversion at constant temperature above the PIT, upon switching the wavelength (Fig. 7.11b). A direct emulsion sample prepared by preirradiation at 436 nm is continuously stirred at constant temperature under permanent visible irradiation. The conductivity (values of the order of mS/cm) remains constant with time. Note that in the absence of stirring, the emulsion appears stable for the typical time of experiments (of the order of a few hours) as long as these irradiation conditions are maintained. However, conductivity displays a sharp decrease after the switch of the wavelength from 436 to 365 nm.The conductivity values of the order of mS/ cm reveal the formation of inverse emulsions that remain stable with time as long as UV irradiation is maintained. Hence, conductivity can be cycled between two plateau values, which correspond to the formation of water and oil continuous emulsions, respectively. Both emulsion type and emulsion stability are well controlled by light and are switched reversibly (Khoukh et al., 2006, 2005).
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7.5. CONCLUSION
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In conclusion, we emphasize the originality and versatility of using azobenzenemodi ed polymers in combination with nanoparticles or micelles. First of all, the various ingredients as well as the methods of preparation and control are now accessible from simple chemistry. Polymer micelle binding affects a rich variety of properties. The ubiquitous role of surfactants in solubilization of particles, formulation of mixtures, surface treatments should be readily controlled in presence of amphiphilic photopolymers. In addition, the stage of ampli cation achieved at the scale of the polymer micelle association could be extended to a more general concept, toward the design of unconventional light-responsive systems of nanoparticles. Minor tailoring efforts are needed to obtain other complexes involving a few azobenzene groups per bound particle, or photochromes other than azobenzenes so as to broaden the eld of applications. As an example, the vast potential of using proteins and enzymes instead of micelles of surfactants is underlined here. Light-triggered association with enzymes have been investigated to trigger a biological activity with light (Lee et al., 2005; Willner and Rubin, 1996). The design of photopolymer capable of binding onto hydrophobic pockets onto enzyme deserves investigation because it would enable one to tune enzyme immobilization and activity with no need for a speci c synthesis or modi cation. The triggering of biodigestion or speci c consumption of substrates in gels and microchips would become readily accessible. This opens up new opportunities for the development of clean active systems for in vivo preparations. Furthermore, a remarkably low density of photochromes (0.5% 3 mol% of monomers) is suf cient, and actually required to confer appropriate sensitivity to
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CHAPTER 7: ASSOCIATION BETWEEN AZOBENZENE MODIFIED POLYMERS
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light of polymer nanoparticle complexes. A low concentration of photochrome (and low absorbances of samples) then becomes compatible with high magnitude of responses. High ef ciency at low absorbance opens the way to unexplored short response times in complex uids (high intensities of light can reach the bulk of samples). For instance, gels and colloid assemblies made photoswitchable on time scale of the order of diffusive times are expected to exhibit new nonequilibrium properties such as photocontrolled morphologies of precipitates (Klajn et al., 2007; Bell and Piech, 2006), or new sorting principles in analytical chemistry (Alcor et al., 2004). The length scale of stimulation can be focused down to micron size. All these features are of great potential bene t in microsystems and micro uidic applications to add a new route toward formation of gradients, modi cation of ow rates, etc. to the present devices based on local applications of heat or of electric eld. Finally, a second stage of ampli cation is recruited when the polymer complexes are close to a critical transition, including solubility, sol gel transition, or adsorption onto interfaces. Light can certainly be used to investigate the dynamics of such complex transitions. Practically, irradiation can be seen as a reversible target-selective tool that requires no extra additive to modify with short pulses of lights (shorter than characteristic diffusion times of the macromolecules) the properties of macromolecules and trigger the variation of interfacial properties (e.g., wettability), release/encapsulation or the continuous phase (e.g., when an emulsion swings between O/W and W/O). Study of the phototriggered dynamics and intermediate stages of phenomena becomes quite readily accessible with azocontaining polymer systems.
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