Photo-induced

The radical cation of 1 (T ) is produced by a photo-induced electron transfer reaction with an excited electron acceptor, chloranil. The major product observed in the CIDNP spectrum is the regenerated electron donor, 1. The parameters for Kaptein s net effect rule in this case are that the RP is from a triplet precursor (p. is +), the recombination product is that which is under consideration (e is +) and Ag is negative. This leaves the sign of the hyperfine coupling constant as the only unknown in the expression for the polarization phase. Roth et aJ [10] used the phase and intensity of each signal to detemiine the relative signs and magnitudes of the... 

There are, indeed, many biological implications that have been triggered by the advent of fullerenes. They range from potential inhibition of HIV-1 protease, synthesis of dmgs for photodynamic therapy and free radical scavenging (antioxidants), to participation in photo-induced DNA scission processes [156, 157, 158, 159, 160, 161, 162 and 163]. These examples unequivocally demonstrate the particular importance of water-soluble fullerenes and are summarized in a few excellent reviews [141, 1751. 

Figure C 1.2.9. Schematic representation of photo induced electron transfer events in fullerene based donor-acceptor arrays (i) from a TTF donor moiety to a singlet excited fullerene and (ii) from a mthenium excited MLCT state to the ground state fullerene.

Fig. 12. Photo-induced chemistry of a 4-sulfonyl DNQ. The intermediate species reacts with adventitious water in the resist film to produce a sulfonic acid...

A second degradation process is oxidation, often photo-induced especially by exposure to light not filtered for uv. The radicals resulting from this reaction promote depolymerization of the cellulose, as well as yellowing and fa ding of paper and media. Aging causes paper to become more crystalline and fragile, and this can be exacerbated particularly if the paper is subjected to poor conditions. 

Thermal or photo-induced decompositions of dialkyl peroxides in the presence of suitable substrates yield various products. For example, with nitric oxides, alkyl nitrites or nitrates are formed and, with carbon monoxide, Z fZ-alkyl esters are obtained (44) ... 

Since the optical transitions near the HOMO-LUMO gap are symmetry-forbidden for electric dipole transitions, and their absorption strengths are consequently very low, study of the absorption edge in Ceo is difficult from both an experimental and theoretical standpoint. To add to this difficulty, Ceo is strongly photosensitive, so that unless measurements arc made under low light intensities, photo-induced chemical reactions take place, in some cases giving rise to irreversible structural changes and polymerization of the... 

Instead of using thermal energy to trigger the hydrogen abstraction mechanism, photo-induced reactions can be also be used to successfully crosslink acrylic PSAs [74-76], In this case, photoactive compounds, such as for example those containing benzophenone, anthraquinone or triazine nuclei are compounded with the polymer or copolymerized as one of the monomers. After drying, the adhesive... 

Reaction Mechanism of Vinyl Polymerization with Amine in Redox and Photo-Induced Charge-Transfer Initiation Systems... 

A substantial number of photo-induced charge transfer polymerizations have been known to proceed through N-vinylcarbazole (VCZ) as an electron-donor monomer, but much less attention was paid to the polymerization of acrylic monomer as an electron receptor in the presence of amine as donor. The photo-induced charge-transfer polymerization of electron-attracting monomers, such as methyl acrylate(MA) and acrylonitrile (AN), have been recently studied [4]. In this paper, some results of our research on the reaction mechanism of vinyl polymerization with amine in redox and photo-induced charge transfer initiation systems are reviewed. 

III. PHOTO-INDUCED CHARGE TRANSFER POLYMERIZATION OF VINYL MONOMERS... 

The photo-induced process of modification of cellulose and its derivatives was reported by Geacintov and coworkers [67,68]. Thus, acrylonitrile, vinyl acetate, styrene, MMA, and the binary system of styrene and AN were grafted onto cellulose and cellulose derivatives. In... 

Photo-induced grafting onto wood cellulose with several vinyl monomers using phenyl acetophenone and benzophenone derivatives as photosensitizers has been reported [72]. A fast increase in grafting was observed for short irradiation times, whereas longer ones resulted in a decreased percent grafting. 

The mechanistic details of photo-induced grafting of styrene onto cellulose in the presence of mineral acids with methanol and dioxane as solvents was investigated... 

Graft Copolymerization of Vinyl Monomers Onto Macromolecules Having Active Pendant Group via Ceric Ion Redox or Photo-Induced Charge-Transfer Initiation... 

MACROMOLECULES HAVING AN ACTIVE PENDANT GROUP BY PHOTO-INDUCED CHARGE-TRANSFER INITIATION... 

Therefore, the graft copolymerization of vinyl monomers onto macromolecules having active an pendant group can be achieved either by redox initiation with a Ce(IV) ion or by photo-induced charge-transfer initiation with BP, depending on the structure of the active groups. 

The excellent agreement between the TSC and P1A results has two implications. First, since the TSC method probes the product of mobility and carrier density, while the P1A probes only the carrier density, there seems to be no dominant influence of temperature on the carrier mobility. This was also found in other conjugated polymers like /ra/ry-polyacetylene [19, 36]. Second, photoconductivity (observed via the thermal release of photoexcited and trapped earners) and photo-induced absorption probe the same charged entity [36, 37J. 

MEH-PPV and P3MBET, were used. As a measure of the efficiency of the photo-induced charge transfer, the degree of luminescence quenching and the ratio of the charged photoexcitation bands to the neutral photoexcitation bands were taken. These two numbers are plotted in Figure 15-15 versus the electrochemical reduction potential. A maximum in the photoinduced electron transfer was determined for Cbo. 

Our journey begins with the photo-induced union of 3,4-dimethylfuran (19) and / -(benzyloxy)-propanal (18) (see Scheme 5). Irradiation of a solution of these two simple, achiral compounds in benzene with a 450 W Hanovia lamp equipped with a vycor filter results in the exclusive formation of head-to-head, exo photoadduct 17 in 63% yield. As a cw-fused dioxabicyclo[3.2.0]heptene system, intermediate 17 possesses a folded molecular framework to which access is obstructed on the concave face. In the presence of mCPBA, the less hindered convex face of the enol ether double bond is oxidized in a completely diastereoselective fashion, affording intermediate 16 in 80% yield after regioselective opening of... 

Scheme 6. Photo-induced bridging of bis(thiolactones) synthesis of dithiatopazine (31), the first stable 1,2-dithietane.

As attractive as the transannular bridging of bis(thiolactones) to bicyclic bis(oxepane) frameworks is, our inability to convert the disulfide bridging product (see 25, Scheme 5) to a mmv-fused bre-vetoxin-type bis(oxepane) (see 28) necessitated the development of a modified, stepwise strategy. This new stepwise approach actually comprises two very effective methods for the construction of cyclic ethers the first of these is the intramolecular photo-induced coupling of dithioesters, and the second is the reductive cyclization of hydroxy ketones. We will first address the important features of both cyclization strategies, and then show how the combination of the two can provide an effective solution to the problem posed by trans-fused bis(oxepanes). 

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