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protein with transfer of a potassium ion from the intercellular fluid into the cell. The overall process corresponds to the scheme Nao+ ATP + ATPase

For the synthesis of azobenzene-containing amphiphilic BCPs, the most used method, which is also the most convenient one, is the atom transfer radical polymerization (ATRP). The rst work was reported in 2002 by Tian et al. who used a hydrophilic poly(ethylene oxide) (PEO) macroinitiator to grow a hydrophobic block of poly{11-[4-(4-butylphenylazo)phenoxy]undecyl methacrylate} that is a side-chain liquid crystalline (LC) polymer (SCLCP) (structure a in Fig. 6.2) (Tian et al., 2002). Even though this amphiphilic BCP was not synthesized and investigated for its self-assembly behavior in solution, PEO is actually a good choice as the hydrophilic block for BCP micelles having interest for possible biomedical applications. PEO is highly soluble in water, enables steric stabilization of the micelle and can inhibit the surface adsorption of biological substances, thus protecting the loaded guest (Kang et al., 2005). Following this work, a number of amphiphilic azobenzene BCPs have been synthesized using PEO macroinitiators with different azobenzene polymers (Ding et al., 2008; Yu et al., 2007a,b, 2006a,b;

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(where the subscripts designate: i, intracellular and o, extracellular). The active form of the enzyme is, in fact, a dimer situated in the phospholipid region of the cytoplasmic membrane (Fig. 6.16) and the ATP molecule is bound between both the macromolecules. This important enzyme is responsible, for example, for the active

Sin et al., 2005; Yu et al., 2005). Using a dibromo initiator, a dibromo PEO macroinitiator (Br-PEO-Br) was prepared and subsequently employed to grow an azobenzene polymer, yielding an amphiphilic ABA-type triblock copolymer (Tang et al., 2007). When other water-soluble polymers are used as the hydrophilic block, the direct synthesis of the hydrophilic macroinitiator using ATRP may be problematic, in contrast to PEO. For instance, ATRP cannot be used to prepare a poly(acrylic acid) macroinitiator because of the reaction between the monomer and the metal complexes (Patten and Matyjaszewski, 1998). The general approach employed to bypass the problem is to synthesize rst a diblock copolymer that is not amphiphilic and, subsequently, convert one block into the desired hydrophilic polymer through a postreaction. As a matter of fact, the rst light-controllable azobenzene BCP micelle was demonstrated using a BCP whose hydrophilic block was obtained in this fashion (structure b in Fig. 6.2) (Wang et al., 2004). A macroinitiator of poly(tert-butyl acrylate) (PtBA) was rst synthesized and then used to grow poly{6-[4-(4-methoxyphenylazo)phenoxy]hexyl methacroylate} (PAzoMA). The resulting diblock copolymer PtBA-b-PAzoMA was rendered amphiphilic by subsequent hydrolysis of PtBA giving rise to the hydrophilic poly(acrylic acid) (PAA). The selective cleavage of tBA groups is possible because

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