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He in (Van Cott et al, 2002), and Barrett (Mermut and Barrett, 2003; Mermut et al, 2003) In some cases, copolymers are synthesized, where some of the repeat units are charged groups and some are azo chromophores (Suzuki et al, 2003; Wu et al, 2001a) These materials may, however, have solubility issues, as the azo chromophore is typically not water-soluble Efforts have therefore gone into synthesizing azo ionomers (Jung et al, 2002; Hong et al, 2000), or polymers where the charge appears on the azobenzene unit (Wang et al, 1998, 2004; Wu et al, 2001a) The azobenzene chromophore may also be created by postfunctionalization of an assembled PEM (Lee et al, 2000) Azobenzene-functionalized PEMs have demonstrated all of the unique photophysics associated with the chromophore, including induced birefringence (Ishikawa et al.



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, 2002; Park and Advincula, 2002) and surface mass transport (Wang et al, 1998) (which is described in more detail in Section 13) It should be noted, however, that in general the quality of the patterning is lower (Wang et al, 2004), presumably because of the constraints to chain motion that the ionic cross-links engender There are many examples of performing the multilayering with a polyelectrolyte and a small molecule azobenzene ionic dye (Dragan et al, 2003) In contrast to conventional doped systems, the chromophores in these systems do not suffer from aggregation instabilities (Advincula et al, 2001), and the azo photomotions do couple to the matrix, as evidenced by birefringence (dos Santos Jr et al, 2003; Bian et al, 2000) and surface patterning (He et al, 2000a,b).

1 2 3 4 5 6 7 8 9 #include <ncurses.h> int main(void) { int y,x,a,b; char ch; char s[] = Excuse me while I squeeze in here! ; initscr();

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These effects can again be attributed to the fact that the ionic attachment points act as cross-links in a dry PEM sample The aggregation and photochemical behavior of the azo chromophore (absorbance spectrum, isomerization rate, etc) vary depending on the nature of the counterpolymer (Dante et al, 1999) (and of course, is affected by any ionic ring substituent) These may be viewed as undesirable matrix effects, or as a way to tune the chromophore response The multilayering technique does not offer the precision and reproducibility of conventional inorganic lm preparation techniques It is, however, simple, versatile, and offers the possibility of combining unique structures and functionalities (for instance, it has been used to create superhydrophobic surfaces [Zhai et al, 2004], to make azo photochromic hollow shells [Jung et al, 2002], and is amenable to patterning [Nyamjav and Ivanisevic, 2004]).

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