Photoisomerizable components

The physical and chemical properties of photoisomerizable molecular films or photoisomerizable polymers are controlled by light. Photochemical control of the formation of liquid crystal phases, or sol-gel transitions,137 381 of polymers containing photoisomerizable components demonstrates signal regulation of the structure and properties of microscopic and macroscopic phases. Physicochemical properties of photoisomerizable membrane-mimetic assemblies such as liposomes,1241 mono-... 

A further approach to controlling electrical communication between redox proteins and their electrode support through a photo-command interface includes photo stimulated electrostatic control over the electrical contact between the redox enzyme and the electrode in the presence of a diffusional electron mediator (Scheme 12).[58] A mixed monolayer, consisting of the photoisomerizable thiolated nitrospiropyran units 30 and the semi-synthetic FAD cofactor 25, was assembled on an Au electrode. Apo-glucose oxidase was reconstituted onto the surface FAD sites to yield an aligned enzyme-layered electrode. The surface-reconstituted enzyme (2 x 10-12 mole cm-2) by itself lacked electrical communication with the electrode. In the presence of the positively charged, protonated diffusional electron mediator l-[l-(dimethylamino)ethyl]ferrocene 29, however, the bioelectrocatalytic functions of the enzyme-layered electrode could be activated and controlled by the photoisomerizable component co-immobilized in the monolayer assembly (Figure 12). In the... 

The immobilization of photoisomerizable host molecules onto an electrode surface can be used for the construction of novel ion-selective electrodes. A photoisomerizable calix[4]arene derivative was incorporated into a polymeric membrane on an electrode surface and the two different isomeric states of the host molecule provided responses selective to Li" or Na" ions depending on the state.Another photoisomerizable host molecule has been constructed from spiropyran and crown-ether subunits. Different binding affinities for Li were found depending on the isomeric state of the photoisomerizable component (26). The researchers suggested that this effect was caused by the coordination of the Li ion to the 0 of the zwitterionic merocyanine-form (Figure 7.29). The photocontrolled host molecules were immobilized in a polymeric film onto an electrode surface, resulting in a photochemically switchable ion-selective electrode. 

In another example, a mixed monolayer composed of a photoisomerizable component and an electrochemical catalyst was applied to switch the electrocatalytic properties of a modified electrode between ON - and OFF -states. A gold electrode surface functionalized with a spiropyran-monolayer and pyrroloquinoline quinone (PQQ) moieties incorporated into the mono-layer was applied to control the electrocatalytic oxidation of NADH by light [92]. The positively charged merocyanine-state interface resulted in the repulsion of Ca2+ cations (promoters for the NADH oxidation by the PQQ), thus resulting in the inhibition of the electrocatalytic process. In the nitrospiropyran-state the monolayer does not prevent association of the PQQ-catalyst and Ca2+-promoter, so provides efficient electrocatalytic oxidation of NADH. Similar results have been achieved by a combination of the photo- and thermal effects resulting in the isomerization of the spiropyran-monolayer with the incorporated PQQ-catalyst [93], Other photoisomerizable materials such as an azobenzenealkanethiol derivative mixed with a ferrocene-redox component have also been used to control the electrocatalyzed electron transfer process between a command interface and a dissolved redox probe [94]. 

The photoswitchable complexation/dissociation properties of n donor-acceptor complexes between xanthene dyes and photoisomerizable bipyrid-inium salts have been used to generate an optoelectronic interface [97] (Fig. 28). Eosin isothiocyanate (52) was covalently linked to an electrode surface via a thiourea bond (Fig. 28A). The electron acceptor 3, 3 -bis(N-methylpyridinium) azobenzene 53 was used as the photoisomerizable component. The association constants of the n donor-acceptor complexes generated between eosin and 53a or 53b in solution correspond to Ka — 8.3 x 103 M-1 and Ka — 3.4 x 103 M 1, respectively. The analysis of complexation on the functionalized surface was accomplished by quartz crystal microbalance measurements. The frequency change (Af) of a piezoelectric quartz crystal on which a mass change Am occurs is given by the Sauerbrey equation (Eqn. 1) ... 

An interesting example of a system whose components become mechanically bound upon surface immobilization is rotaxane trans-21 (Fig. 13.24), consisting of a ferrocene-functionalized /3-cyclodextrin (fi-CD) macrocycle threaded on a molecule containing a photoisomerizable azobenzene unity and a long alkyl chain.33 A monolayer of trans-21 was self-assembled on a gold electrode. Therefore, the ring... 

Equation was derived without approximations. It is noteworthy that these solutions do not couple tensorial components of different orders and that they confirm that rotational diffusion and cis—>trans thermal isomerization are isotropic processes that do not favor any spatial direction. In Section 3.4, I discuss, through the example of azobenzene, how Equation 3.11 can be used to study reorientation processes during cis—>trans thermal isomerization after the end of irradiation. The next subsection gives analytical expressions at the early-time evolution and steady-state of photo-orientation, for the full quantification of coupled photo-orientation and photoisomerization in A<- B photoisomerizable systems where B is unknown. 

Affinity Interactions at Interfaces Using Soluble Photoisomerizable Guest Components... 

INTERLOCKED COMPOUNDS AS MECHANICAL COMPONENTS AT PHOtOiSOMERIZABLE INTERFACES... 

The immobilization of a photoisomerizable material that can be switched by light between redox-active and redox-inactive or conductive and insulating states offers an encouraging route toward integrated molecular memory devices. Figure 7.2 shows a photoisomer state A in which the molecular unit is redox-inactive and no electronic signal is transduced. Photoisomerization of the chemical component to state B generates a redox-active assembly, and the electron transfer between the electrode and the chemical modifier yields an amperometric (electrochemical) indicator of the state of the system. 

RECOGNITION PHENOMENA AT SURFACES USING PHOTOISOMERIZABLE GUEST OR HOST COMPONENTS... 

Figure 7,26 shows the reversible association of a photoisomerizable guest to a chemically modified surface. In configuration A of the molecular component, no affinity interactions with the modified surface exist, and the system is in a mute state. Photoisomerization of the substrate to state B activates the affinity binding of the molecular component to the surface. The binding interaction may then be transduced by electronic, optical, or spectroscopic means. 

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