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cohydrolysis and cocondensation of azobenzene-containing organosilanes with other silica precursors, such as tetraethyl orthosilicate (TEOS). 13.3.1.1. Preparation of Photoresponsive Mesoporous Materials. Brinker and coworkers prepared photoresponsive thin lm nanocomposites via an EISA procedure using the nonionic surfactant Brij 56 or the triblock copolymer surfactant P123 as structure-directing agents (Liu, 2004; Liu et al., 2003a). In the EISA process, TSUA is mixed with TEOS in a homogeneous ethanol water solution. The amphiphilic nature of the hydrolyzed TSUA molecule positions the hydrophobic propylureidoazobenzene groups in the hydrophobic micellar cores and the silicic acid groups coorganize with hydrolyzed TEOS moieties at the hydrophilic micellar exteriors. In this fashion, TSUA is ultimately incorporated on the pore surfaces with the azobenzene ligands disposed toward the pore interiors. Subsequent solvent extraction results in a mesoporous silica framework modi ed with azobenzene ligands, which are isomerizable by light and thermal stimuli (Fig. 13.8). The dimensional change of the propylureidoazobenzene ligand associated with this isomerization mechanism is estimated to be 3.4 A on the basis of molecular modeling with Chem3Dt 5.5 software (Cambridgesoft).



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N OT E Here s a tip: Familiarize yourself with the editor s command that instantly jumps to a specific line number. Most of your editing will actually be re-editing, where the compiler directs you to a specific line number. If you know the line-number-jumping command, you can get there quickly to fix your source code and try (again) to compile it:

In vim, the line number skipping command is nG, where n is the line number and G is Shift+G. Thus, typing 6G will get you right to line 6.

Figure 13.8. Photoresponsive nanocomposites prepared by EISA. The trans or cis conformation of azobenzene unit was calculated using Chem3D Prot (Cambridgesoft) molecular modeling analysis software. Source: From Liu et al., 2003a. Reprinted with permission.

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A POA manager is invoked in the call chain before any servant manager, and has no influence on the selection of the remote object. POA managers are optionally created on the call to PortableServer::POA::create_POA and are associated with one or more POAs.

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Brinker and coworkers also prepared photoresponsive nanoporous silica particles using aerosol-assisted assembly, EISA, and surfactant-directed selfassembly (SDSA) techniques (Liu, 2004). The as-prepared photoresponsive nanocomposite particles were prepared so that the azobenzene ligands pointed toward the hydrophobic micellar interiors. After surfactant removal by solvent extraction, nanoporous particles with azobenzene ligands positioned on the pore surfaces were formed (Fig. 13.8). Corriu and coworkers prepared several kinds of hybrid materials using BSPA as the azobenzene-containing precursor, including a xerogel monolith and thin lms with (or without) structure-directing agents (Besson et al., 2005). The xerogel monolith was prepared by hydrolysis and cocondensation of BSPA with TEOS (19 equivalent) at pH = 1.5 using a nonionic triblock polymer P123 surfactant as the template. Thin lm samples were deposited on silicon wafers by dip-coating a sol-containing BSPA, TEOS (19 equivalent), HCl, H2O, P123, and EtOH in EISA process. The postgrafting method was also utilized to functionalize mesoporous silica materials with azobenzene moieties. Zink and coworkers prepared a series of azobenzene-containing dendrons from G0 to G3 (Fig. 13.9) and tethered them to the nanoporous silica materials using a three-step synthetic procedure (Sierocki et al., 2006). First, nanostructured silica materials were synthesized according to the well-developed SDSA approach (Kresge et al., 1992) and the EISA technique (Brinker et al., 1999). Then, the pore surfaces of the nanostructured silica were modi ed with isocyanopropyltriethoxysilane (ICPES) through a vapor deposition

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CORBA Technology Projection The following state diagram shows the various states in which the POA manager can exist.

Figure 13.9. Chemical structures of the azobenzene-containing dendrons. The number 0, 1, 2, and 3 notations within the phenyl rings indicate the number of generations (AzoG0 AzoG3).

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