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Figure 13.18. The I t behavior of a Brij 56 templated photoresponsive nanocomposite lm under alternate exposure to UV (360 nm) and visible light (435 nm) using various molecular probes. (a) FDM. Inset is the absorbance of the same lm at 356 nm attributed to the p p* transition of the trans isomer. The time scale of the UV/visible data corresponds to that of the rst cycle in I t response curve. (b) FDMDG. (c) FDMTG.

BladeCenter (general purpose)

(m') = E (m') - ^r l n *A-(1) = (m') - \r foA-(0 " PA 0)]

architecture is not an artifact of the ITO electrode or mesoporous silica lm but a true effect due to the isomerization of azobenzene moieties attached to the nanopore surfaces To correlate the observed current changes with the actual isomerization state, a UV/visible spectroscopy study was performed, where the nanocomposite lm used for chronoamperometry was immersed in the electrolyte solution and illuminated in the same manner as the rst I t cycle in the chronoamperometry experiment As shown in the inset, Fig 1318a, the absorbance of the nanocomposite lm at 355 nm (lmax of p p* transition of azobenzene in trans form) decreases progressively under UV (l = 360 nm) irradiation and reaches a plateau, which corresponds to the photostationary state of the trans-cis isomerization The following visible light (l = 435 nm) exposure causes the reverse cis-trans isomerization, increasing the absorbance gradually before reaching the pre-UV state.

where Ep is the electrode potential of the ideal polarized electrode on the hydrogen scale (this is a generalization of the electrode potential; see Section 3.1.5). The surface charge densities a(m) for the metal phase and a(l) for the

These data exactly correlate to the conformational changes of azobenzene moieties in the nanocomposite lm with the oxidative current changes measured in the chronoamperometry experiment This demonstrates for the rst time optical control of mass transport through a nanocomposite thin lm To investigate the in uence of the size of the probing molecules on mass transport, FDMDG and FDMTG were synthesized according to a previously reported procedure (Lindner et al, 2001) and chronoamperometry experiments were performed using FDMDG and FDMTG as the molecular probes The I t curves (Fig 1318b,c) of the photoresponsive nanocomposite lms show similar photoresponses to those of the FDM probe, that is, the oxidative current increases under UV light (360 nm) irradiation and decreases under visible light (435 nm) exposure However, the oxidative current cannot reach steady state but decreases gradually to a very low value (o0.

BladeCenter H (high performance) BladeCenter T (Telco - ruggedized) HS20 - Intel Xeon HS20 ULP HS21 - Intel Dual Core Xeon LS20 - AMD Opteron Microsoft Windows, Red Hat Linux, Novell, Novell NetWare, Turbolinux Microsoft Windows, Red Hat Linux, Novell SUSE Microsoft Windows, Red Hat Linux, Novell, Novell NetWare Microsoft Windows, Microsoft Windows3, WinXP, Red Hat Linux, Novell, Novell NetWare Microsoft Windows, Red Hat Linux, Novell, Novell NetWare, Sun Solaris Microsoft Windows, Red Hat Linux, Novell, Novell NetWare, Sun Solaris IBM AIX, Novell SUSE Linux, Red Hat Linux IBM AIX, Novell SUSE Linux, Red Hat Linux IBM AIX, Novell SUSE Linux, Red Hat Linux Yes Yes Yes Yes

1= 1

05 mA) because of the adsorption of the probe molecules and their oxidative species The strong hydrogen-bonding interaction between the ethylene glycol groups in the probe molecules and the silanol ( OH), urea ( NH CO NH ), and azo groups ( NQN ) on the silica wall and the electrostatic interaction between the positively charged oxidative species of the probe molecules and negatively charged silica wall lead to the adsorption of the probe molecules and accumulation of the oxidative species on the ITO electrode surface and, correspondingly, a decrease in the current In comparison to the hydrogen-bonding interaction, the electrostatic interaction is not predominant because of the low charge density on the silica wall in the azobenzenemodi ed nanocomposite membranes As a support, steady-state oxidative current can be reached with an FDM probe that has no ethoxy groups because of less hydrogen-bonding interaction.

(4.2.20)

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The Connolly solvent excluded volumes (the volume contained within the contact molecular surface) of the probe molecules are 269 A3, 392 A3, and 515 A3 for FDM, FDMDG, and FDMTG, respectively It is clear that increasing the volume of the probe molecule lowers the overall mass transport, thereby decreasing the oxidative current, but increases the selectivity as evidenced by the greater normalized current ratio (DI/Iss)..

It holds in the metal phase that jUM(m) = 4- jUe(m) and in the salt phase MA (denoted r) that //MAO) = /WO) + A -(r). As fiM(m) and / / M A W are constants and because at equilibrium jUA-(r) = /iA-(l), jUM+(r) = MM+(m')> it follows that d M+(m) + dAc(m) = 0 d M+(m') + d/iA-(l) = < W 0 ) F d0(l) dA(m') = 0

Yes (CSM)

jUM+(m)