Photo-active

Merlic et al. were the first to predict that exposing a dienylcarbene complex 126 to photolysis would lead to an ort/zo-substituted phenolic product 129 [74a]. This photochemical benzannulation reaction, which provides products complementary to the classical para-substituted phenol as benzannulation product, can be applied to (alkoxy- and aminocarbene)pentacarbonyl complexes [74]. A mechanism proposed for this photochemical reaction is shown in Scheme 54. Photo activation promotes CO insertion resulting in the chromium ketene in-... 

Scheme 54 Complementary benzannulation via photo activation of carbonyl ligands...

CBz-protected benzimidazole gave primarily oxazinone [31], while 3/f-indoles incorporated two equivalents of imine (Eq. 4) [32]. In these cases it appears that the initially formed zwitterionic ketene-imine adduct could not close, and reacted with additional photo activated carbene or substrate. 

Photo-induced Diels Alder reaction occurs either by direct photo activation of a diene or dienophile or by irradiation of a photosensitizer (Rose Bengal, Methylene Blue, hematoporphyrin, tetraphenylporphyrin) that interacts with diene or dienophile. These processes produce an electronically excited reagent (energy transfer) or a radical cation (electron transfer) or a radical (hydrogen abstraction) that is subsequently trapped by the other reagent. 

Abstract In this paper the synthesis, properties and applications of poly(organophos-phazenes) have been highlighted. Five different classes of macromolecules have been described, i.e. phosphazene fluoroelastomers, aryloxy-substituted polymeric flame-retardants, alkoxy-substituted phosphazene electric conductors, biomaterials and photo-inert and/or photo-active phosphazene derivatives. Perspectives of future developments in this field are briefly discussed. 

Thus, the photo-activity of poly[bis(4-benzoylphenoxy)phosphazene] under illumination could be finely tuned by irradiating the polymer in the presence of variable amount of naphthalene, a typical triplet state energy quencher [474]. The same polymer could be used as polymeric photosensitizer to induce the... 

This chapter presents an overview of the synthesis, ensemble photoluminescence properties and blinking of single CdSe quantum dots. The stress is on (i) widely accepted methods of synthesis, (ii) the origin of photoluminescence and variations of photoluminescence as functions of surface-coating, surface-passivating molecules, chemical environment, and thermal- and photo-activations, and (iii) photolumines-... 

S., Grzesiek, S., litman, B. J., Bax, A. Measurement of dipolar couplings in a transdudn peptide fragment weakly bound to oriented photo-activated rhodopsin. f. Biomol. NMR 2000, 16, 121-125. 

Fig. 44. Common sites for attaching redox- and photo-active groups to nucleosides C5 pyrimidine, C7-deaza-purine, and C8-purine.

Fig 46. On-column attachment of redox- and photo-active groups to DNA oligomers. Reproduced with permission from Ref. (159). Copyright 1999, American Chemical Society. 

UV degradation is a chemical destruction process which leads, under short-wave light, to the direct oxidation of the binder by means of atmospheric oxygen. The reaction takes place mainly via photo-activated states of the binder macromolecules. 

Organometallic dendrimers have been constructed to act as potential electro-or photo-active materials, the synthesis of which will be discussed in the following section. Apart from the examples discussed above, surface modification of dendrimers with a variety of functional groups has afforded novel redox active materials [110-116]. 

Fig. 13 Schematic representation of a photo-active molecular junction containing DAE-based SAM sandwiched between a semitransparent Au bottom electrode and an SAM/Hg-drop top electrode. The electrical response of the junction is measured upon irradiation at different wavelengths through the semitransparent bottom electrode...

Nuclear science in particular obtains from laser-driven electron sources a brand new input to perform interesting measurements in the context of many laboratories equipped with ultrashort powerful lasers. The ultrashort duration of these particle bunches represent a further attractive feature for these kinds of studies. In the following, we will focus on nuclear reaction induced by gamma radiation produced by bremsstrahlung of laser-produced electrons in suitable radiator targets. This way is usually mentioned as photo-activation and is particularly efficient for photons of energy close to the Giant Dipole Resonance of many nuclei. 

Figure 9.20 The photo-activated process that accounts for vision the 11-cis — 11-trans photo-isomerism of retinal...

Size, shape, and density The shielding effects of dendritic shells can likewise be caused by steric factors. Thus, the access of foreign molecules to the central functional unit can be hindered or prevented according to size and density of the dendritic shell. Sometimes, even a certain size selectivity is observed. These effects are especially interesting for electrochemically, catalytically active, redox-and photo-active functional units, since interactions with foreign molecules, such as oxygen quenching of the luminescence (photo-active units) or the access of substrates (catalytically active units) can be influenced.14 11 17,221... 

P.R. Ashton, R. Ballardini, V. Balzani, A. Credi, M. T. Gandolfi, D. J.-F. Marquis, S. Menzer, L. Perez-Garcia, L. Prodi, J. E Stoddart, M. Venturi, A. J. P. White, D. J. Williams, The Self-Assembly of [2]Catenanes Incorporating Photo-Active and Electro-Active re-Extended Systems , J. Am. Chem. Soc 1995,117,11171-11197. 

In a more simple and cheap way, silver clusters can be prepared in aqueous solutions of commercially available polyelectrolytes, such as poly(methacrylic acid) (PM A A) by photo activation using visible light [20] or UV light [29]. Ras et al. found that photoactivation with visible light results in fluorescent silver cluster solutions without any noticeable silver nanoparticle impurities, as seen in electron microscopy and from the absence of plasmon absorption bands near 400 nm (F = 5-6%). It was seen that using PMAA in its acidic form, different ratios Ag+ MAA (0.15 1-3 1) lead to different emission bands, as discussed in the next section (Fig. 12) [20]. When solutions of PMAA in its sodium form and silver salt were reduced with UV light (365 nm, 8 W), silver nanoclusters were obtained with emission band centered at 620 nm and [Pg.322]

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