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2 10 6 s 1), whereas the bulkier AzoG3 dendron had the slowest reaction (26 10 6 s 1) This result is not surprising because the smaller AzoG0 has more freedom to isomerize within the con ned space of the MCM-41 materials The azobenzene derivatives require an extra volume of at least 127 A3 to undergo complete isomerization (Victor and Torkelson, 1987) For the bulky AzoG3 dendron, the con ned space hinders the conformational change of the azobenzene ligands The thermal cis-trans isomerization of the azobenzene ligands con ned in the nanopores has a constant rate constant and exhibits faster isomerization than in solution with the exception of the bulky AzoG3 dendrimer This result is consistent with Brinker and coworkers observation of azobenzene-modi ed nanoporous silica lms and supports their two-rate-constant physical model The nanoporous silica materials prepared by Brinker and coworkers have a cubic (BCC) pore structure.



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The azobenzene ligands positioned on the pore connections have different local environments from those positioned on the spherical pore surfaces Thus the azobenzene ligands isomerize at two different rates fast and slow The MCM-41 nanoporous materials prepared by Zink and coworkers have a hexagonal array pore structure in which all the azobenzene ligands positioned on the channel surfaces have the same local environment Thus simple one-rateconstant rst-order kinetics is suf cient to describe the isomerization process 13323 Photoisomerization of Bridged Azobenzene Ligands in Mesoporous Silica Materials Corriu and coworkers found that for thin lm samples using P123 surfactant templates, BSPA incorporated into a silica matrix exhibited similar reversible photoisomerization to that in solution (Besson et al, 2005).

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However, for BSPA TEOS co-gel thin lm samples without P123 template and pure BSPA gel lms, the azobenzene moieties showed no change in the UV/visible spectra under UV light irradiation, indicating hindered photoisomerization This observation is consistent with Brinker and coworkers ndings on the hybrid silica materials prepared using azobenzene-bridged organosilane (BSUA) In Brinker s case (Liu et al, 2002), the hydrogen-bonding interaction between the urea groups not only self-assembles BSUA into highly ordered lamellar structures but also locks in the structures and hinders the photoisomerization of the azobenzene ligands Only after dilution of BSUA with TEOS and.

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Over the years, escape speeds have been slowly increasing. Table 8.1 shows the percentage of ejections occurring at or above given speeds. The Hunter was tted with a Martin Baker MK4 ejection seat and was typical of the aircraft in service from the mid 1950s to the mid 1970s. The Tornado is tted with a Martin Baker Mk10 ejection seat and is typical of aircraft in service from the mid 1970s to today. These are predominantly peacetime ejections, in wartime ejection speeds tend to increase overall. Table 8.1 Comparison of ejection speeds

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HMDS to prevent the close packing of the BSUA molecules did the azobenzene ligands exhibit reversible photoisomerization. In Corriu s case, the BSPA/TEOS co-gel lms and the pure BSPA gel lms did not exhibit photoisomerization because of the lack of suf cient space for isomerization or the close packing of azobenzene ligands in the lm. The P123-templated nanoporous lms prepared using BSPA and TEOS precursors exhibited similar photoisomerization to those in solution because the removal of the surfactant molecules provided large free volume for the isomerization of the azobenzene ligands positioned on the pore surfaces.

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Nanovalves are devices that can regulate mass transport at the nanoscale by means of light, pH, heat, or other external stimuli Mesoporous materials provide an excellent platform for constructing the nanovalves because of their sizecontrollable nanoscale pores and versatile surface chemistries In an effort to make such devices, Mal et al (2003a,b) synthesized coumarin-modi ed MCM-41 mesoporous silica powders that showed reversible control of release of guest molecules (cholestane) using UV light (l = 250 nm) A team led by Stoddart and Zink built nanovalves that can regulate the controlled-release of guest molecules from nanoporous silica particles using redox-controllable bistable[2]rotaxane molecules (Nguyen et al, 2005; Hernandez et al, 2004) or pH-controllable supermolecules (Leung et al, 2006; Nguyen et al, 2006) to switch the opening and closing of nanopores Azobenzene derivatives have also been used to control mass transport through lipid bilayer membranes 13331.

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Photocontrolled Transport Phenomenon in Lipid Bilayer Membranes Photocontrolled ion transport across lipid bilayer membranes using photoresponsive compounds such as azobenzene derivatives has been of great interest for potential applications in optoelectronic devices and optical transducers Most research has exploited membrane capacitance change because of the disruption of membrane structures resulting from photoisomerization of azobenzene-containing compounds incorporated into the lipid bilayers Others have used the volumetric change of azobenzene moieties associated with photoisomerization In the 1990s, Yonezawa and coworkers pioneered the studies on the photoresponses of planar black lipid membranes containing an amphiphilic azobenzene derivative, 4-octyl-4u-(5-carbox-pentamethylene-oxy) azobenzene (8A5) (Tanaka and Yonezawa, 1997; Tanaka et al, 1996a,b, 1995; Fujiwara and Yonezawa, 1991) After 8A5 was inserted into the lipid membrane, transient current pulses were generated under alternating irradiation of UV and visible light This method was chosen because of the lipid membrane s capacity change induced by azobenzene trans2cis photoisomerization (Fig.

Aircraft Hunter Tornado 350 Kts 19% 36% 400 Kts 8% 16% 450 Kts 4% 8%

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